Little, Alastair, Pellis, Alessandro, Comerford, James William orcid.org/0000-0002-9977-5695 et al. (4 more authors) (2020) Effects of Methyl Branching on the Properties and Performance of Furandioate-Adipate Copolyesters of Bio-Based Secondary Diols. ACS Sustainable Chemistry & Engineering. 14471–14483. ISSN 2168-0485
Abstract
Furandioate-adipate copolyesters are an emerging class of bio-based biodegradable polymers with great potential to replace fossil-derived terephthalic acid-based copolyesters such as poly(butylene adipate-co-terephthalate) (PBAT). Furandioate-adipate polyesters have almost exclusively been prepared with conventional primary (1°) alcohol diols, while secondary (2°) alcohol diol monomers have largely been overlooked until now, despite preliminary observations that using methyl-branched diols increases the Tg of the resultant polyesters. Little is known of what impact the use of 2° alcohol diols has on other properties such as material strength, hydrophobicity, and rate of enzymatic hydrolysis—all key parameters for performance and end-of-life. To ascertain the effects of using 2° diols on the properties of furandioate-adipate copolyesters, a series of polymers from diethyl adipate (DEA) and 2,5-furandicarboxylic acid diethyl ester (FDEE) using different 1° and 2° alcohol diols was prepared. Longer transesterification times and greater excesses of diol (diol/diester molar ratio of 2:1) were found to be necessary to achieve Mws > 20 kDa using 2° alcohol diols. All copolyesters from 2° diols were entirely amorphous and exhibited higher Tgs than their linear equivalents from 1° diols. Compared to linear poly(1,4-butyleneadipate-co-1,4-butylenefurandioate), methyl-branched, poly(2,5-hexamethyleneadipate-co-2,5-hexamethylenefurandioate) (0:7:0.3 furandioate/adipate ratio) displayed both higher modulus (67.8 vs 19.1 MPa) and higher extension at break (89.7 vs 44.5 mm). All other methyl-branched copolyesters displayed lower modulus but retained higher extension at break compared with their linear analogues. Enzymatic hydrolysis studies using Humicola insolens cutinase revealed that copolyesters from 2° alcohol diols have significantly decreased rates of biodegradation than their linear equivalents synthesized using 1° alcohol diols, allowing for fine-tuning of polymer stability. Hydrophobicity, as revealed by water contact angles, was also found to generally increase through the introduction of methyl branching, demonstrating potential for these materials in coatings applications.
Metadata
Item Type: | Article |
---|---|
Authors/Creators: |
|
Copyright, Publisher and Additional Information: | © 2020 American Chemical Society |
Keywords: | Bio-based polymers,5-(chloromethyl)furfural,adipic acid,secondary alcohol diols,2,5-furandicarboxylic acid |
Dates: |
|
Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Funding Information: | Funder Grant number BBSRC (BIOTECHNOLOGY AND BIOLOGICAL SCIENCES RESEARCH COUNCIL) BB/N023595/1 EPSRC EP/L017393/1 |
Depositing User: | Pure (York) |
Date Deposited: | 04 Nov 2020 09:30 |
Last Modified: | 22 Jan 2025 00:15 |
Published Version: | https://doi.org/10.1021/acssuschemeng.0c04513 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1021/acssuschemeng.0c04513 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:167588 |
Download
Filename: effectofmethylbranchingonF_Apolyesters_MASCAL_FARMER_2020.pdf
Description: effectofmethylbranchingonF-Apolyesters_MASCAL&FARMER_2020
Licence: CC-BY 2.5