Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters
The enzymatic synthesis of polyesters in solventless systems is an environmentally friendly and sustainable method for synthetizing bio-derived materials. Despite the greenness of the technique, in most cases only short oligoesters are obtained, with limited practical applications or requiring furth...
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ftdoajarticles:oai:doaj.org/article:e4431fe8aa054634b0fa273bfe6b05fa 2023-05-15T13:40:17+02:00 Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters James W. Comerford Fergal P. Byrne Simone Weinberger Thomas J. Farmer Georg M. Guebitz Lucia Gardossi Alessandro Pellis 2020-01-01T00:00:00Z https://doi.org/10.3390/ma13020368 https://doaj.org/article/e4431fe8aa054634b0fa273bfe6b05fa EN eng MDPI AG https://www.mdpi.com/1996-1944/13/2/368 https://doaj.org/toc/1996-1944 1996-1944 doi:10.3390/ma13020368 https://doaj.org/article/e4431fe8aa054634b0fa273bfe6b05fa Materials, Vol 13, Iss 2, p 368 (2020) bio-based polyesters enzymatic synthesis polycondensation thermal upgrade metal-free synthesis biocatalyzed process solventless reactions Technology T Electrical engineering. Electronics. Nuclear engineering TK1-9971 Engineering (General). Civil engineering (General) TA1-2040 Microscopy QH201-278.5 Descriptive and experimental mechanics QC120-168.85 article 2020 ftdoajarticles https://doi.org/10.3390/ma13020368 2022-12-31T00:47:33Z The enzymatic synthesis of polyesters in solventless systems is an environmentally friendly and sustainable method for synthetizing bio-derived materials. Despite the greenness of the technique, in most cases only short oligoesters are obtained, with limited practical applications or requiring further chemical processing for their elongation. In this work, we present a catalyst-free thermal upgrade of enzymatically synthesized oligoesters. Different aliphatic and aromatic oligoesters were synthesized using immobilized Candida antarctica lipase B (iCaLB) as the catalyst (70 °C, 24 h) yielding poly(1,4-butylene adipate) (PBA, M w = 2200), poly(1,4-butylene isophthalate) (PBI, M w = 1000), poly(1,4-butylene 2,5-furandicarboxylate) (PBF, M w = 600), and poly(1,4-butylene 2,4-pyridinedicarboxylate) (PBP, M w = 1000). These polyesters were successfully thermally treated to obtain an increase in M w of 8.5, 2.6, 3.3, and 2.7 folds, respectively. This investigation focused on the most successful upgrade, poly(1,4-butylene adipate), then discussed the possible effect of di-ester monomers as compared to di-acids in the thermally driven polycondensation. The herein-described two-step synthesis method represents a practical and cost-effective way to synthesize higher-molecular-weight polymers without the use of toxic metal catalysts such as titanium(IV) tert -butoxide, tin(II) 2-ethylhexanoate, and in particular, antimony(IV) oxide. At the same time, the method allows for the extension of the number of reuses of the biocatalyst by preventing its exposure to extreme denaturating conditions. Article in Journal/Newspaper Antarc* Antarctica Directory of Open Access Journals: DOAJ Articles Materials 13 2 368 |
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Open Polar |
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Directory of Open Access Journals: DOAJ Articles |
op_collection_id |
ftdoajarticles |
language |
English |
topic |
bio-based polyesters enzymatic synthesis polycondensation thermal upgrade metal-free synthesis biocatalyzed process solventless reactions Technology T Electrical engineering. Electronics. Nuclear engineering TK1-9971 Engineering (General). Civil engineering (General) TA1-2040 Microscopy QH201-278.5 Descriptive and experimental mechanics QC120-168.85 |
spellingShingle |
bio-based polyesters enzymatic synthesis polycondensation thermal upgrade metal-free synthesis biocatalyzed process solventless reactions Technology T Electrical engineering. Electronics. Nuclear engineering TK1-9971 Engineering (General). Civil engineering (General) TA1-2040 Microscopy QH201-278.5 Descriptive and experimental mechanics QC120-168.85 James W. Comerford Fergal P. Byrne Simone Weinberger Thomas J. Farmer Georg M. Guebitz Lucia Gardossi Alessandro Pellis Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters |
topic_facet |
bio-based polyesters enzymatic synthesis polycondensation thermal upgrade metal-free synthesis biocatalyzed process solventless reactions Technology T Electrical engineering. Electronics. Nuclear engineering TK1-9971 Engineering (General). Civil engineering (General) TA1-2040 Microscopy QH201-278.5 Descriptive and experimental mechanics QC120-168.85 |
description |
The enzymatic synthesis of polyesters in solventless systems is an environmentally friendly and sustainable method for synthetizing bio-derived materials. Despite the greenness of the technique, in most cases only short oligoesters are obtained, with limited practical applications or requiring further chemical processing for their elongation. In this work, we present a catalyst-free thermal upgrade of enzymatically synthesized oligoesters. Different aliphatic and aromatic oligoesters were synthesized using immobilized Candida antarctica lipase B (iCaLB) as the catalyst (70 °C, 24 h) yielding poly(1,4-butylene adipate) (PBA, M w = 2200), poly(1,4-butylene isophthalate) (PBI, M w = 1000), poly(1,4-butylene 2,5-furandicarboxylate) (PBF, M w = 600), and poly(1,4-butylene 2,4-pyridinedicarboxylate) (PBP, M w = 1000). These polyesters were successfully thermally treated to obtain an increase in M w of 8.5, 2.6, 3.3, and 2.7 folds, respectively. This investigation focused on the most successful upgrade, poly(1,4-butylene adipate), then discussed the possible effect of di-ester monomers as compared to di-acids in the thermally driven polycondensation. The herein-described two-step synthesis method represents a practical and cost-effective way to synthesize higher-molecular-weight polymers without the use of toxic metal catalysts such as titanium(IV) tert -butoxide, tin(II) 2-ethylhexanoate, and in particular, antimony(IV) oxide. At the same time, the method allows for the extension of the number of reuses of the biocatalyst by preventing its exposure to extreme denaturating conditions. |
format |
Article in Journal/Newspaper |
author |
James W. Comerford Fergal P. Byrne Simone Weinberger Thomas J. Farmer Georg M. Guebitz Lucia Gardossi Alessandro Pellis |
author_facet |
James W. Comerford Fergal P. Byrne Simone Weinberger Thomas J. Farmer Georg M. Guebitz Lucia Gardossi Alessandro Pellis |
author_sort |
James W. Comerford |
title |
Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters |
title_short |
Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters |
title_full |
Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters |
title_fullStr |
Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters |
title_full_unstemmed |
Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters |
title_sort |
thermal upgrade of enzymatically synthesized aliphatic and aromatic oligoesters |
publisher |
MDPI AG |
publishDate |
2020 |
url |
https://doi.org/10.3390/ma13020368 https://doaj.org/article/e4431fe8aa054634b0fa273bfe6b05fa |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
Materials, Vol 13, Iss 2, p 368 (2020) |
op_relation |
https://www.mdpi.com/1996-1944/13/2/368 https://doaj.org/toc/1996-1944 1996-1944 doi:10.3390/ma13020368 https://doaj.org/article/e4431fe8aa054634b0fa273bfe6b05fa |
op_doi |
https://doi.org/10.3390/ma13020368 |
container_title |
Materials |
container_volume |
13 |
container_issue |
2 |
container_start_page |
368 |
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1766131819149787136 |