Glycerol-based enzymatically synthesized renewable polyesters: Control of molecular weight, degree of branching and functional endgroups
[EN] The catalytic specificity of Lipase B from Candida antarctica (CALB) has been exploited to achieve specific terminal groups for the synthesis of glycerol poly(ester)s. This permits the preparation of glycerol-derived macromers able to undergo further reactions/chemical modifications for customi...
Published in: | European Polymer Journal |
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Main Authors: | , , , , |
Other Authors: | , , , , |
Format: | Article in Journal/Newspaper |
Language: | English |
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Elsevier
2022
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Online Access: | http://hdl.handle.net/10251/199569 https://doi.org/10.1016/j.eurpolymj.2022.111173 |
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ftunivpvalencia:oai:riunet.upv.es:10251/199569 |
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record_format |
openpolar |
institution |
Open Polar |
collection |
Politechnical University of Valencia: RiuNet |
op_collection_id |
ftunivpvalencia |
language |
English |
topic |
Enzyme-catalyzed polymerization CALB Poly (glycerol adipate) Branching degree Endgroups CIENCIA DE LOS MATERIALES E INGENIERIA METALURGICA |
spellingShingle |
Enzyme-catalyzed polymerization CALB Poly (glycerol adipate) Branching degree Endgroups CIENCIA DE LOS MATERIALES E INGENIERIA METALURGICA Sonseca Olalla, Agueda Hevilla Talavera, Víctor López García, Daniel Giménez Torres, Enrique Fernández García, Marta Glycerol-based enzymatically synthesized renewable polyesters: Control of molecular weight, degree of branching and functional endgroups |
topic_facet |
Enzyme-catalyzed polymerization CALB Poly (glycerol adipate) Branching degree Endgroups CIENCIA DE LOS MATERIALES E INGENIERIA METALURGICA |
description |
[EN] The catalytic specificity of Lipase B from Candida antarctica (CALB) has been exploited to achieve specific terminal groups for the synthesis of glycerol poly(ester)s. This permits the preparation of glycerol-derived macromers able to undergo further reactions/chemical modifications for customization as functional systems and building blocks for polymer synthesis. Poly(glycerol adipate) based macromers with different terminal structures were achieved from the reaction between glycerol and divinyl adipate by varying the stoichiometry (from equimolar to 1.5 and 3.0 excess either of glycerol or divinyl adipate) and amount of catalyst (1 and 3 wt%). In the course of polymerization, transesterification and hydrolysis reactions occur over vinyl functionalities that result in acid endgroups. Thus, the resulting macromers are either terminated with hydroxyl groups and/or acid groups and/or vinyl groups. Therefore, an understanding of how acid functionality appears (from vinyl groups hydrolysis) and its quantification under various conditions may provide an opportunity for the design of synthetic strategies to avoid acid production and obtain the desired structures. Endgroup analysis was carried out using 1H NMR and 13C NMR spectroscopies and MALDI-TOF spectrometry. Mainly linear hydroxyl and vinyl-terminated macromers were obtained with high efficiency without significant hydrolysis of the chain ends (for vinyl terminated). This work was funded by the GVA (GV/2021/182), the MICINN (PID2019-104600RB-100), the Agencia Estatal de Investigacion (AEI, Spain), and Fondo Europeo de Desarrollo Regional (FEDER, EU). A. S. acknowledges her "APOSTD/2018/228" and "PAID-10-19" postdoctoral contracts from Culture and Sport Council from the Government of Valencia and from the Polytechnic University of Valencia, respectively. Sonseca Olalla, A.; Hevilla Talavera, V.; López García, D.; Giménez Torres, E.; Fernández García, M. (2022). Glycerol-based enzymatically synthesized renewable polyesters: Control of molecular weight, ... |
author2 |
Universitat Politècnica de València. Escuela Técnica Superior de Ingenieros Industriales - Escola Tècnica Superior d'Enginyers Industrials Universitat Politècnica de València. Escuela Técnica Superior de Ingeniería del Diseño - Escola Tècnica Superior d'Enginyeria del Disseny Agencia Estatal de Investigación Generalitat Valenciana Universitat Politècnica de València |
format |
Article in Journal/Newspaper |
author |
Sonseca Olalla, Agueda Hevilla Talavera, Víctor López García, Daniel Giménez Torres, Enrique Fernández García, Marta |
author_facet |
Sonseca Olalla, Agueda Hevilla Talavera, Víctor López García, Daniel Giménez Torres, Enrique Fernández García, Marta |
author_sort |
Sonseca Olalla, Agueda |
title |
Glycerol-based enzymatically synthesized renewable polyesters: Control of molecular weight, degree of branching and functional endgroups |
title_short |
Glycerol-based enzymatically synthesized renewable polyesters: Control of molecular weight, degree of branching and functional endgroups |
title_full |
Glycerol-based enzymatically synthesized renewable polyesters: Control of molecular weight, degree of branching and functional endgroups |
title_fullStr |
Glycerol-based enzymatically synthesized renewable polyesters: Control of molecular weight, degree of branching and functional endgroups |
title_full_unstemmed |
Glycerol-based enzymatically synthesized renewable polyesters: Control of molecular weight, degree of branching and functional endgroups |
title_sort |
glycerol-based enzymatically synthesized renewable polyesters: control of molecular weight, degree of branching and functional endgroups |
publisher |
Elsevier |
publishDate |
2022 |
url |
http://hdl.handle.net/10251/199569 https://doi.org/10.1016/j.eurpolymj.2022.111173 |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_relation |
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http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
op_doi |
https://doi.org/10.1016/j.eurpolymj.2022.111173 |
container_title |
European Polymer Journal |
container_volume |
170 |
container_start_page |
111173 |
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ftunivpvalencia:oai:riunet.upv.es:10251/199569 2024-01-28T10:01:27+01:00 Glycerol-based enzymatically synthesized renewable polyesters: Control of molecular weight, degree of branching and functional endgroups Sonseca Olalla, Agueda Hevilla Talavera, Víctor López García, Daniel Giménez Torres, Enrique Fernández García, Marta Universitat Politècnica de València. Escuela Técnica Superior de Ingenieros Industriales - Escola Tècnica Superior d'Enginyers Industrials Universitat Politècnica de València. Escuela Técnica Superior de Ingeniería del Diseño - Escola Tècnica Superior d'Enginyeria del Disseny Agencia Estatal de Investigación Generalitat Valenciana Universitat Politècnica de València 2022 http://hdl.handle.net/10251/199569 https://doi.org/10.1016/j.eurpolymj.2022.111173 eng eng Elsevier European Polymer Journal info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-104600RB-I00/ES/POLIMEROS SOSTENIBLES BIOBASADOS CON ACTIVIDAD ANTIMICROBIANA/ info:eu-repo/grantAgreement/GVA/Programa para la promoción de la investigación científica, el desarrollo tecnológico y la innovación en la Comunitat Valenciana/GV%2F2021%2F182/ES/subvenciones a grupos de investigación emergentes info:eu-repo/grantAgreement/GVA//APOSTD%2F2018%2F228/ info:eu-repo/grantAgreement/UPV//PAID-10-19 https://doi.org/10.1016/j.eurpolymj.2022.111173 10.1016/j.tibtech.2020.02.001 10.1016/j.fuel.2019.116553 10.3390/catal10111279 10.1016/j.progpolymsci.2012.02.001 10.1016/j.progpolymsci.2014.11.002 10.1002/marc.201400389 10.1016/j.eurpolymj.2018.09.032 10.1002/mabi.202100156 10.3390/ijms20246210 10.1021/acs.biomac.5b00018 10.1002/pi.1994.210330101 10.1016/j.polymer.2014.08.036 10.1016/j.polymer.2005.02.046 10.1021/acs.biomac.6b01224 10.1246/cl.2000.800 10.1021/ma0612834 10.1021/ma0351827 10.1021/ja9808907 10.1002/1616-5195(200101)1:1 40::AID-MABI40>3.0.CO;2-T 10.3390/polym8030080 10.1021/bm000097h 10.1016/j.polymer.2016.02.036 10.1021/bm049200j 10.3390/polym11101561 10.3390/polym12122969 10.1039/C0PY00340A 10.1039/C4PY01223B 10.1016/j.biomaterials.2015.10.037 10.1002/pola.23887 10.1021/acs.iecr.9b03869 10.37155/2717-526X-0201-1 10.1002/mabi.201500284 10.1002/(SICI)1097-0290(19970705)55:1 227::AID-BIT23>3.0.CO;2-H 10.1002/(SICI)1097-4628(19980411)68:2 173::AID-APP1>3.0.CO;2-N 10.1016/S0141-0229(03)00064-4 10.1016/j.molcatb.2004.10.003 10.1246/cl.1994.1687 10.1039/p19930000899 10.1002/(SICI)1099-0518(19990801)37:15 2737::AID-POLA7>3.0.CO;2-M 10.1002/mrc.1260270611 10.1021/ma0480190 10.3390/polym4010396 10.1016/j.eurpolymj.2012.11.011 10.1021/bk-2013-1135.ch004 http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess Enzyme-catalyzed polymerization CALB Poly (glycerol adipate) Branching degree Endgroups CIENCIA DE LOS MATERIALES E INGENIERIA METALURGICA info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion 2022 ftunivpvalencia https://doi.org/10.1016/j.eurpolymj.2022.111173 2024-01-03T00:07:39Z [EN] The catalytic specificity of Lipase B from Candida antarctica (CALB) has been exploited to achieve specific terminal groups for the synthesis of glycerol poly(ester)s. This permits the preparation of glycerol-derived macromers able to undergo further reactions/chemical modifications for customization as functional systems and building blocks for polymer synthesis. Poly(glycerol adipate) based macromers with different terminal structures were achieved from the reaction between glycerol and divinyl adipate by varying the stoichiometry (from equimolar to 1.5 and 3.0 excess either of glycerol or divinyl adipate) and amount of catalyst (1 and 3 wt%). In the course of polymerization, transesterification and hydrolysis reactions occur over vinyl functionalities that result in acid endgroups. Thus, the resulting macromers are either terminated with hydroxyl groups and/or acid groups and/or vinyl groups. Therefore, an understanding of how acid functionality appears (from vinyl groups hydrolysis) and its quantification under various conditions may provide an opportunity for the design of synthetic strategies to avoid acid production and obtain the desired structures. Endgroup analysis was carried out using 1H NMR and 13C NMR spectroscopies and MALDI-TOF spectrometry. Mainly linear hydroxyl and vinyl-terminated macromers were obtained with high efficiency without significant hydrolysis of the chain ends (for vinyl terminated). This work was funded by the GVA (GV/2021/182), the MICINN (PID2019-104600RB-100), the Agencia Estatal de Investigacion (AEI, Spain), and Fondo Europeo de Desarrollo Regional (FEDER, EU). A. S. acknowledges her "APOSTD/2018/228" and "PAID-10-19" postdoctoral contracts from Culture and Sport Council from the Government of Valencia and from the Polytechnic University of Valencia, respectively. Sonseca Olalla, A.; Hevilla Talavera, V.; López García, D.; Giménez Torres, E.; Fernández García, M. (2022). Glycerol-based enzymatically synthesized renewable polyesters: Control of molecular weight, ... Article in Journal/Newspaper Antarc* Antarctica Politechnical University of Valencia: RiuNet European Polymer Journal 170 111173 |