Polyesters containing cyclic carbohydrate-based units obtained by ring opening polymerization

• Main Author: Morales Huerta, Juan Carlos
• Other Authors: Universitat Politècnica de Catalunya. Departament d'Enginyeria Química, Muñoz Guerra, Sebastián, Martínez de Ilarduya Sáez de Asteasu, Domingo Antxon
• Format: Doctoral or Postdoctoral Thesis
• Language: English
• Published: Universitat Politècnica de Catalunya 2018
• Subjects: Àrees temàtiques de la UPC::Enginyeria química; Polyesters; Carbohydrates; Bio-based; Cyclic oligoesters; Ring opening polymerization; Furan-based polyesters; Poly(butylene 2,5-furandicarboxylate); Antarc*; Antarctica
• Online Access: http://hdl.handle.net/2117/115040; http://hdl.handle.net/10803/462146; https://doi.org/10.5821/dissertation-2117-115040

Premi extraordinari doctorat UPC curs 2017-2018. Àmbit d’Enginyeria Industrial In recent years, as a result of climate change, the interest in sustainable materials has increased dramatically. The replacement of compounds of petrochemical origin by bio-based has spread to all areas of chemistry. Nowadays there is a development of sustainable polymers based in 2,5-furanedicarboxylic acid (FDCA) as it may compete in performance with the ones based on terephthalic acid (PTA). On the other hand, the entropically driven ring opening polymerization (ED-ROP) is an attractive synthesis route whose interest has grown in this last decade because the reaction is athermal, no byproducts are generated and polymers of high molecular weight can be obtained in short reaction times. This Thesis reports the synthesis and characterization of cyclic oligomers of FDCA with different diols, such as 1,4-butanediol (c(BF)n), ethylene glycol (c(EF)n), resorcinol (c(RF)n) and isomannide (c(ImF)n) using different synthetic routes including high dilution condensation (HDC) and cyclodepolymerization (CD). The cyclic oligomers of butylene isophthalate (c(BI)n) and butylene terephthalate (c(BT)n) have also been synthesized by HDC. Finally, the cyclic oligomers of butylene succinate (c(BS)n) and ethylene succinate (c(ES)n) were obtained by enzymatic cyclization reaction (EC). The furanic cyclic oligomers were homopolymerized and copolymerized with the aforementioned cyclic oligoesters as well as with epsilon-caprolactone (e-CL). The polymerization reactions were catalyzed with tin octanoate (SnOct2), except in the case of homopolyesters and copolyesters with aliphatic units in which the Candida antarctica lipase B (CALB) was used. The molecular weights of the polymers obtained ranged between 25,000 and 80,000 g / mol. The copolymers presented a random microstructure with the exception of the caprolactone derivatives, which presented a blocky microstructure. Differential scanning calorimetry (DSC) studies revealed that PEF, PBF, PBT, PBI, ...