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

Resumen

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, PBS, PES, and their copolymers with less than 30% of aliphatic comonomer, turned out to be crystalline, on the contrary, copolymers with close compositions to 50:50 were usually amorphous. On the other hand, the PRF and the PImF were amorphous and the incorporation of their units in other copolyesters restricted the their crystallinity. In addition, the melting temperature (Tm) and the glass transition temperature (Tg) were intermediate to those of the homopolyesters, with a practically linear tendency in the second case. The crystallizability of most copolyesters was also studied, which allowed obtaining different kinetic parameters through the application of the Avrami equation. Thermogravimetric analysis (TGA) revealed that most polyesters and copolyesters were thermally stable up to 400 oC. The studies of hydrolytic and enzymatic degradability showed the high resistance to the degradation of PBF, PEF and PRF, which decreased markedly with the incorporation of aliphatic units such as BS, ES, CL or ImF in the copolyesters. This thesis summarizes the main aspects in the synthesis of cyclic oligomers of FDCA and its homopolymerization and copolymerization with different cyclic oligomers via ED-ROP. According to the results obtained, polyesters based on furanic derivatives could be considered as a viable alternative to polyesters of petrochemical origin for industrial applications.