Macromolecules, Vol.45, No.20, 8257-8266, 2012
Bio-Based Aromatic Polyesters from a Novel Bicyclic Diol Derived from D-Mannitol
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 degrees C. They displayed outstanding high T-g with values from 55 to 137 degrees 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.