Renewable terephthalate polyesters from carbohydrate-based bicyclic monomers

Abstract

Poly(alkylene terephthalate)s, PET and PBT in particular, are materials of great relevance and growing projection in the thermoplastic field but are today almost totally produced from fossil resources. The current huge consumption of these polyesters necessitates urgent actions addressed to make them renewable by using naturally-occurring raw materials. Among the different approaches that are being followed to develop bio-based poly(terephthalate)s, the use of bicyclic carbohydrate-derived difunctional compounds as building-blocks is receiving much attention in the last few years because partially renewable polyesters with high Tg may be thus obtained. This review presents a critical account of the terephthalate homopolymers and copolymers that have been synthesized using the two types of carbohydrate-based bicyclic monomers, isohexides and diacetals, explored to date. The properties displayed by the novel bio-based poly(terephthalate)s in relation to the bicyclic structure of the used monomers are comparatively reviewed and their potential as emergent materials for thermoplastic applications is evaluated.Peer ReviewedPostprint (published version

Chemical Structure and Microstructure of Poly(alkylene terephthalate)s, their Copolyesters, and their Blends as Studied by NMR

“…Above T g , the polyester tends to lose stiffness and dimensional stability if no fillers are added, which makes it less suitable for applications involving elevated temperatures. Copolymerization with structurally stiff diols has been the approach of choice to address this problem . However, copolymerization entails a significant reduction in the crystallinity and crystallizability of PBT, which is in most cases undesirable.…”

Toward replacement of styrene by bio-based methacrylates in unsaturated polyester resins

“…Noteworthy, blends of classical vinyl esters with these candidates yielded thermosets owing Tg comparable to those of commercial VER thermosets. Other methacrylic-type candidates can be envisioned from biobased building blocks derived from carbohydrates that can be isolated from numerous feedstocks (e.g., starch, cellulose, hemicellulose or lignin) 14 . For instance, furoic acid glycidyl methacrylate (FA-GM) or furfuryl methacrylate (FM) have been used in conjunction with commercial VE prepolymer 15 .…”

Lipase‐Catalyzed Synthesis of Furan‐Based Oligoesters and their Self‐Assembly‐Assisted Polymerization

“…[13,54,55] Specifically, only af ew reports are available on the lipase-catalyzed polycondensation of furan-based monomers. Bifunctional monomer 3a possesses two primary hydroxyl groups along with three secondary hydroxy groups, whereas 3b and 3c each have one primary hydroxy and carboxylic acidg roup.…”