Isomannide-Containing Poly(butylene 2,5-furandicarboxylate) Copolyesters via Ring Opening Polymerization

Abstract

Cyclic oligomers of isomannide 2,5-furandicarboxylate were synthesized using the high dilution condensation method. A mixture of dimer, trimer and tetramer species largely enriched in the dimer was obtained. These cyclic oligomers were copolymerized with those made of butylene 2,5-furandicarboxylate in bulk at 220 º C by ring opening polymerization using Sn(Oct) 2 as catalyst. A series of random poly(butylene 2,5-furandicarboxylate) copolyesters containing isomannide in a range of 5 to 50 %-mole and with weight-average molecular weights between 30,000 and 50,000 g•mol-1 were prepared. These copolyesters started to decompose above 300 ºC and only those containing less than 10 %-mole of isomannide showed signs of crystallinity. They displayed glass-transition temperatures in the 40-100 ºC range with values increasing steadily with the content in isomannide. At difference with the poly(butylene 2,5-furandicarboxylate) homopolyester that is reluctant to hydrolysis, the isomannide-containing copolyesters were noticeably degraded by water, much more rapidly when exposed to the presence of lipases.

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

“…The vast majority of these copolymers were prepared by melt polycondensation reactions at high temperatures. 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 ].…”

“…The research group of Dr. Muñoz-Guerra has synthesized various furanoate-containing cyclic oligomers (mixtures of dimers, trimers, and tetramers mainly) and copolymerized them by entropically-driven ROP ( Scheme 2 ) [ 64 , 66 , 69 , 83 , 86 , 105 ]. One of the advantages of ROP is the high polymerization rate, which results in relatively milder conditions and shorter reaction times compared to traditional two-step melt polycondensations.…”

“…The structure of the obtained copolymers was mostly random, indicating that extensive transesterification reactions take place concomitantly with ROP. Copolymers with CL and isomannide units tended to exhibit a more blocky structure, depending on the feed ratio [ 66 ].…”

“…However, this small biodegradation is important, as these copolymers do not contain aliphatic dicarboxylic acids, but both repeating units have a furan ring. Similarly, PImF showed up to 50% mass loss during enzymatic hydrolysis, and the corresponding PBF-PImF copolymers were also biodegradable [ 66 ]. Poly(ester carbonate)s PIsF-PBF-PIC-PBS with high molecular weights were noticeably degradable in comparison with PBF, and that biodegradation originated from the butylene succinate and the butylene carbonate units [ 70 ].…”

Low‐crystallinity to highly amorphous copolyesters with high glass transition temperatures based on rigid carbohydrate‐derived building blocks

“…Although the oxy-heterocyclic FDCA molecule exhibits a higher hydrophilicity than terephthalic acid, PBF homopolyester remains highly resistant to biodegradation under natural environmental conditions or lipase-catalyzed conditions (37°C, pH 7.4). 35 Our previous study regarding the (bio)degradability of terephthalic acid-based copolyesters showed that the presence of IS moieties enhances the hydrolytic degradation of the polymers to a certain extent, yet insignificantly influences their biodegradation properties. 23 For PBIF copolyesters, the crystallinities are much inhibited which, together with the high hydrophilicity of the materials, might result in degradable polyesters with enhanced thermal properties.…”