Co-Polymers based on Poly(1,4-butylene 2,5-furandicarboxylate) and Poly(propylene oxide) with Tuneable Thermal Properties: Synthesis and Characterization

Abstract

Poly(ether ester)s (PEEs) represent a promising class of segmented co-polymers, nevertheless the synthesis of PEEs based on renewable 2,5-furandicarboxylic acid (FDCA) is still scarce. In this context, a series of poly(1,4-butylene 2,5-furandicarboxylate)-co-poly(poly(propylene oxide) 2,5-furandicarboxylate) co-polyesters with different composition of stiff poly(1,4-butylene 2,5-furandicarboxylate) (PBF) and soft poly(poly(propylene oxide) 2,5-furandicarboxylate) (PPOF) moieties were synthesized, via a two-step bulk polytransesterification reaction. The molar ratio of PBF/PPOF incorporated was varied (10 to 50 mol%) in order to prepare several novel materials with tuned properties. The materials were characterised in detail through several techniques, namely ATR FTIR, 1H and 13C NMR, TGA, DSC, DMTA and XRD. Their hydrolytic and enzymatic degradation evaluation was also assessed. These new co-polymers showed either a semi-crystalline nature when higher PBF/PPOF ratios were used, and for approximately equal amounts of PBF and PPOF an amorphous co-polyester was obtained instead.

Microstructure and Mechanical/Elastic Performance of Biobased Poly (Butylene Furanoate)–Block–Poly (Ethylene Oxide) Copolymers: Effect of the Flexible Segment Length

“…As seen in Table 1 the integral intensities of signals d (I d ) and e (I e ), corresponding to the presence of the flexible segment, are changing the most due to their different content in copolymers. The obtained results strictly correspond to the 1 H-NMR results reported for the similar PBF/PEO or PBF/PPO copolymers [18][19][20]. The calculated real contents of the rigid and flexible units are also very close to those theoretically calculated, what confirms once again the expected segmented structure of the copolymers.…”

“…Recently a few studies on PBF block copolymers have been published, in which poly (ethylene oxide) (PEO) or poly (propylene oxide) (PPO) were used as the co-monomers [18][19][20]. The special interest in these building blocks lies in their non-toxicity and biocompatibility [21], that extends the potential applications of the biobased copolymers also for biomedical purposes.…”

Tuning the Properties of Furandicarboxylic Acid-Based Polyesters with Copolymerization: A Review

“…A number of alternative approaches has also been investigated; the synthesis of cyclic furanoate oligomers has allowed for the preparation of furanoate copolymers, notably PBF copolymers, by ring-opening polymerization (ROP) [ 64 , 66 , 83 , 86 , 98 , 105 ]. Additionally, the use of enzymatic polymerization has been employed, which warrants a more sustainable synthetic procedure and milder reaction conditions [ 80 , 86 , 93 ].…”

“…When it comes to the structure of the products, random copolymers are mostly obtained. Block or multiblock copolymers are obtained in copolymers incorporating polyether segments, such as poly(ethylene glycol) (PEG) or poly(tetramethylene glycol) (PTMG) [ 46 , 47 , 48 , 56 , 88 , 89 , 90 , 91 , 93 , 94 , 101 ]. When ROP with CL or lactide is included in the polymerization, the outcome depends on the experimental conditions, and both random [ 49 , 54 , 85 ] and block copolymers [ 54 , 87 , 95 , 98 ] have been obtained.…”

“…The high stiffness of the furan ring can benefit the formation of 2,5-FDCA block copolymers, where the furan-based polyesters act as the hard segment and can be considered as physical crosslinking points. A number of polymers were used in the literature as a soft segment for the creation of 2,5-FDCA-based copolymers such as PEG [ 47 , 48 , 88 , 89 ], poly(tetramethylene glycol) (PTMG) [ 56 , 94 ], PPO [ 93 ], and PLA [ 98 ]. The thermal behavior of these materials is quite similar and heavily dependent on the block length, as well as to the content of each block.…”