The carbohydrate-based diol 2,4:3,5-di-O-methylene-d-mannitol (Manx) has been used to obtain aliphatic polyesters. Manx is a symmetric bicyclic compound consisting of two fused 1,3-dioxane rings and bearing two primary hydroxyl groups. In terms of stiffness, it is comparable to the widely known isosorbide, but it affords the additional advantages of being much more reactive in polycondensation and capable of producing stereoregular polymers with fairly high molecular weights. A fully bio-based homopolyester (PManxS) has been synthesized by polycondensation in the melt from dimethyl succinate and Manx. The high thermal stability of PManxS, its relatively high glass transition temperature (Tg = 68 °C) and elastic modulus, and its enhanced sensitivity to the action of lipases point to PManxS as a polyester of exceptional interest for those applications where biodegradability and molecular stiffness are priority requirements. In addition, random copolyesters (PBxManxyS) covering a broad range of compositions have been obtained using mixtures of Manx and 1,4-butanediol in the reaction with dimethyl succinate. All PBxManxyS were semicrystalline and displayed Tg values from -29 to +51 °C steadily increasing with the content in Manx units. The stress-strain behavior of these copolyesters largely depended on their content in Manx and they were enzymatically degraded faster than PBS.
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http://dx.doi.org/10.1021/bm301854c | DOI Listing |
Int J Mol Sci
January 2025
Academy for Engineering and Technology, Yiwu Research Institute, Zhuhai Fudan Innovation Institute, Fudan University, Shanghai 200433, China.
While the traditional rubber industry faces the severe pressure of environmental pollution and carbon emissions, bio-based and biodegradable elastomers have become a hot topic in the field and drawn intensive research interest. Inspired by polyester resin, incorporating polyol or polycarboxylic acid as a branching unit into aliphatic polyester and/or introducing a monomer with a C=C bond to provide open-bond cross-linking in the fashion of common vulcanization to form three-dimensional network structures are two mainstream strategies for designing biodegradable polyester elastomers (BPEs). Both methods encounter more or fewer problems, such as poor mechanical and thermal properties due to the easy hydrolysis of the ester bond and space hinderance, or the potential harm of the remaining degraded small molecules with olefin bonds.
View Article and Find Full Text PDFGreen Chem
January 2025
Università degli Studi di Genova, Dipartimento di Chimica e Chimica Industriale via Dodecaneso 31 16146 Genova Italy
In this work, three bis-pyrrolidone-based structures (BP) were synthesized combining dimethyl itaconate (DMI), the dimethyl ester derivative of itaconic acid, with various aliphatic diamines having a C4 to C12 carbon chain length with the aim of developing novel bio-based building blocks. All three BPs were obtained with a purity >93% and could further be used without performing any tedious purification step, therefore allowing an easy scalability of the synthesis on a 10 g scale. Their potential application was demonstrated in two key areas of modern polymer science: (1) the enzymatic synthesis of polyesters and (2) their use as poly(lactic acid) (PLA) additives.
View Article and Find Full Text PDFMacromol Rapid Commun
January 2025
School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 62 Nanyang Drive, Singapore, 637459, Singapore.
A series of biomass-based linear aliphatic polyesters are synthesized by combining sebacic acid (SA) (C10 diacid) and 1,18-octadecanedioic acid (OA) (C18 diacid) with a series of diols with varied alkyl chain lengths (C2 to C10 diols). SA and OA are obtainable from castor oil and palm oil, respectively. The reaction extent (polymerization extent) is high (≥96%) in all cases, and the number-average molecular weight (M) is 10 000-43 000 g mol after purification.
View Article and Find Full Text PDFJ Hazard Mater
December 2024
Department of Biology, University of the Balearic Islands, Palma 07122, Spain. Electronic address:
Biodegradable plastics, primarily aliphatic polyesters, degrade to varying extents in different environments. However, the absence of easily implementable techniques for screening microbial biodegradation potential -coupled with the limitations of non-functional omics analyses- has restricted comparative studies across diverse polymer types and ecosystems. In this study, we optimized a novel airbrushing method that facilitates functional analyses by simplifying the preparation of polyester-coated plates for biodegradation screening.
View Article and Find Full Text PDFNat Commun
January 2025
Ecole Polytechnique Fédérale de Lausanne (EPFL), Institute of Materials, Laboratory of Macromolecular and Organic Materials, Lausanne, Switzerland.
The plastic waste crisis is among humanity's most urgent challenges. However, widespread adoption of sustainable plastics is hindered by their often inadequate processing characteristics and performance. Here, we introduce a bio-inspired strategy for the modification of a representative high molar mass, biodegradable aliphatic polyester that helps overcome these limitations and remains effective at molar masses far greater than the entanglement molar mass.
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