Copolyesters Made from 1,4-Butanediol, Sebacic Acid, andd-Glucose by Melt and Enzymatic Polycondensation

Abstract

Biotechnologically accessible 1,4-butanediol and vegetal oil-based diethyl sebacate were copolymerized with bicyclic acetalized D-glucose derivatives (Glux) by polycondensation both in the melt at high temperature and in solution at mild temperature mediated by polymer-supported Candida antarctica lipase B (CALB). Two series of random copolyesters (PB x Glux y Seb and PBSeb x Glux y ) were prepared differing in which D-glucose derivative (Glux diol or Glux diester) was used as comonomer. The three parent homopolyesters PBSeb, PBGlux and PGluxSeb were prepared as well. Both methods were found to be effective for polymerization although significant higher molecular weights were achieved by melt polycondensation. The thermal properties displayed by the copolyesters were largely dependent on composition and also on the functionality of the replacing Glux unit. The thermal stability of PBSeb was retained or even slightly increased after copolymerization with Glux whereas crystallinity and melting temperature were largely depressed. On the contrary, the glass-transition temperature noticeably increased with the content in Glux units. PGluxSeb distinguished in displaying both T g and T m higher than PBSeb because a different crystal structure is adopted by this homopolyester. The hydrolytic degradability of PBSeb in water was enhanced by copolymerization, in particular when biodegradation was assisted by lipases.2

Synthetic Polymers from Sugar-Based Monomers

“…41 During the last 5 years, Munõz-Guerra, Galbis, and coworkers have been reporting on a new series of biodegradable linear polyesters and copolyesters from bicyclic acetalized monosaccharide monomers derived from galactaric acid (58) (Scheme 8), 42,43 D-mannitol (27), 44 D-glucitol (24), and Dglucaric acid (59) (Scheme 9). 45 Homopolyesters and random copolyesters covering a broad range of compositions were obtained. The thermal properties, especially those of the copolyesters, were largely dependent on compositions and also on the functionality of the replacing sugar unit.…”

A biocatalytic approach towards sustainable furanic–aliphatic polyesters

“…[33][34][35][36][37] In recent years, enzymatic synthesis of sustainable polyesters from biobased monomers has attracted much attention. 5,32 Plenty of biobased polyesters have been readily prepared via enzymatic polymerization, e.g., succinate-based aliphatic polyesters, [38][39][40] 1,4 : 3,6-dianhydrohexitol-based polyesters, 41,42 vegetal oilbased polyesters, 43 sugar derived diol-based polyesters, 44,45 etc. Recently we successfully synthesized a series of renewable 2,5-bis(hydroxymethyl)furan-based polyesters by two-stage enzymatic polycondensation in diphenyl ether.…”

Enzymatic Polymerization of Furan-2,5-Dicarboxylic Acid-Based Furanic-Aliphatic Polyamides as Sustainable Alternatives to Polyphthalamides

“…[34][35][36][37] This is mainly due to the high melting temperatures (T m ) and low solubility of polyamides. 33 In our laboratory the hydrolase-catalyzed polymerization is actively investigated and therefore various polyesters and polyamides are successfully produced via enzymatic polymerization, e.g., saturated and unsaturated aliphatic polyesters, [38][39][40] glucose-based polyesters, 41 furan-based polyesters, 42,43 semi-aromatic oligoamides, 44 oligo(amino acid)s, 45 aliphatic polyamides [46][47][48] and poly(amide-co-ester)s. 49 The previous studies reported by our laboratory revealed that Novozym 435 (N435), which is an immobilized form of Candida antarctica Lipase B (CALB) on acrylic resin, is a robust biocatalyst for polyester and polyamide synthesis; and N435 works well with FDCA derivatives in biocatalytic polyester synthesis. 42,43 Based on these results, we are confident that N435 is also capable of catalyzing the polymerization of FDCA derivatives and aliphatic diamines.…”