Bio-Based Aromatic Polyesters from a Novel Bicyclic Diol Derived from d-Mannitol

Abstract

2,4:3,5-Di-O-methylene-D-mannitol, abbreviated as Manx, is a D-mannitol-derived compound with the secondary hydroxyl groups acetalized with formaldehyde. The bicyclic structure of Manx consists of two fused 1,3-dioxane rings, with two primary hydroxyl groups standing free for reaction. A homopolyester made of Manx and dimethyl terephthalate as well as a set of copolyesters of poly(butylene terephthalate) (PBT) in which 1,4-butanediol was replaced by Manx up to 50% were synthesized and characterized. The polyesters had M w in the 30 000−52 000 g mol −1 range and a random microstructure and were thermally stable up to nearly 370°C. They displayed outstanding high T g with values from 55 to 137°C which steadily increased with the content in Manx. Copolyesters containing up to 40% of Manx were semicrystalline and adopted the crystal structure of PBT. Their stress− strain parameters were sensitively affected by the presence of carbohydrate-based units with elongation at break decreasing but tensile strength and elastic moduli steadily increasing with the degree of replacement.

High Thermal Stability of Bio-Based Polycarbonates Containing Cyclic Ketal Moieties

“…The rigidity of the monomer induces the stiffness leading to high glass transition temperature rather than independently linked by single C−C bond, 23 which is critical for the preparation of polymers. 24 Moreover, recent bio-based monomers for improvement of the mechanical and/or the thermal properties of polycarbonates have several steps for preparation, but CaG, as it is synthesized in one step, needs no protection and deprotection steps, and the organic acid catalyst was simply removed by work-up process. The polymerizations involving CaG were carried out in the melt polycondensation conditions applied in the industrial process.…”

Modification of poly(ethylene 2,5-furandicarboxylate) with 1,4-cyclohexanedimethylene: Influence of composition on mechanical and barrier properties

“…Unfortunately, its T g was decreased to only M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT toughness of aliphatic polyesters. For example, the cyclic diol, 2,3:4,5-di-O-methylene-galactitol (Galx) and 2,4:3,5-di-O-methylene-D-mannitol (Manx) have been employed to improve the polyesters chain stiff so as to enhance their T g and mechanical properties [33][34][35][36]. The bio-based isosorbide has also been used as the monomers to modify polyesters [37][38].…”

Bio‐based aromatic copoly(ether ester)s with enhanced toughness and degradability: Influence of insertion of phenoxy‐ether linkage and eugenol‐derived composition on properties

“…More surprisingly, the dispersity values of the copoly(ether ester)s are found to be between 1.7 and 1.9, which are rather low and monotonous compared to our previously reported solely eugenol-based poly(ether ester)s with dispersity values between 1.8 and 2.2, 29 and furthermore carbohydrate-based polyesters with dispersity values ranging from 2.3 to 2.5. 7,8 This result reveals that the two dimethyl ester groups in nipaginderived N1 have the same reactivity which is different from FIGURE 1 The different constitutional resonances of the methylenes adjacent to the hydroxy-oxygens for PDN1 1-x E1 x copoly(ether ester)s with the indications of the dyads to which they are assigned.…”

“…5,6 In recent years, replacing or partial replacing either the diol or the dimethyl ester, or even both, by other biobased monomers is particularly appealing supposing that the typical characteristics of the original materials are not significantly impoverished. [7][8][9] Among the naturally occurring resources, carbohydrates and plant oils stand in the critically important position due to their multifunctional transformation possibilities and as appropriate comonomers for aromatic polyesters extensive studies have also been carried out. [10][11][12][13] Nevertheless, the excessive reactive functional groups and thus caused the complexity of synthetic routes render these comonomers very difficult to be industrialized in a large scale.…”