Experimental Design (2⁴) to Improve the Reaction Conditions of Non-Segmented Poly(ester-urethanes) (PEUs) Derived from α,ω-Hydroxy Telechelic Poly(ε-caprolactone) (HOPCLOH)

Aliphatic unsegmented polyurethanes (PUs) have garnered relatively limited attention in the literature, despite their valuable properties such as UV resistance and biocompatibility, making them suitable for biomedical applications. This study focuses on synthesizing poly(ester-urethanes) (PEUs) usin...

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Autores: Maldonado-Estudillo, Jaime, Navarro Crespo, Rodrigo, Marcos-Fernández, Ángel, Dios Caputto, María Dolores de, Cruz-Jiménez, Gustavo, Báez-García, José Eduardo
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2025
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositório:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/382536
Acesso em linha:http://hdl.handle.net/10261/382536
Access Level:Acceso aberto
Palavra-chave:Experimental design
Poly(ester-urethanes)
Number-average molecular weight
Poly(ε-caprolactone)
Telechelic
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spelling Experimental Design (2⁴) to Improve the Reaction Conditions of Non-Segmented Poly(ester-urethanes) (PEUs) Derived from α,ω-Hydroxy Telechelic Poly(ε-caprolactone) (HOPCLOH)Maldonado-Estudillo, JaimeNavarro Crespo, RodrigoMarcos-Fernández, ÁngelDios Caputto, María Dolores deCruz-Jiménez, GustavoBáez-García, José EduardoExperimental designPoly(ester-urethanes)Number-average molecular weightPoly(ε-caprolactone)TelechelicAliphatic unsegmented polyurethanes (PUs) have garnered relatively limited attention in the literature, despite their valuable properties such as UV resistance and biocompatibility, making them suitable for biomedical applications. This study focuses on synthesizing poly(ester-urethanes) (PEUs) using 1,6-hexamethylene diisocyanate and the macrodiol α,ω-hydroxy telechelic poly(ε-caprolactone) (HOPCLOH). To optimize the synthesis, a statistical experimental design approach was employed, a methodology not commonly utilized in polymer science. The influence of reaction temperature, time, reagent concentrations, and solvent type on the resulting PEUs was investigated. Characterization techniques included FT-IR, <sup>1</sup>H NMR, differential scanning calorimetry (DSC), gel permeation chromatography (GPC), optical microscopy, and mechanical testing. The results demonstrated that all factors significantly impacted the number-average molecular weight (<i>M</i><sub>n</sub>) as determined by GPC. Furthermore, the statistical design revealed crucial interaction effects between factors, such as a dependence between reaction time and temperature. For example, a fixed reaction time of 1 h, with the temperature varying from 50 °C to 61° C, did not significantly alter <i>M</i><sub>n</sub>. Better reaction conditions yielded high <i>M</i><sub>n</sub> (average: 162,000 g/mol), desirable mechanical properties (elongation at break > 1000%), low levels of unreacted HOPCLOH in the PEU films (OH/ESTER response = 0.0008), and reduced crystallinity (Δ<i>H</i><sub>m</sub> = 11 J/g) in the soft segment, as observed by DSC and optical microscopy. In contrast, suboptimal conditions resulted in low <i>M</i><sub>n</sub>, brittle materials with unmeasurable mechanical properties, high crystallinity, and significant amounts of residual HOPCLOH. The best experimental conditions were 61 °C, 0.176 molal, 8 h, and chloroform as the solvent (ε = 4.8).Consejo Nacional de Humanidades Ciencia y Tecnología (CONAHCYT) CF-2023-I-2233 and Sistema Nacional de Investigadores (SNI 2). J.M.-E. thanks the CONAHCYT for the scholarship (No. 782319); European Fund under the ERASMUS-EDU-2022-PI-ALL-INNO-BLUEPRINT project, reference number 101103234 (ChemSkills) and the Ministry of Science, Innovation and Universities for the funding received through the PID2023-147542OB-I00, CPP2023-010769 grants.Peer reviewedMultidisciplinary Digital Publishing InstituteConsejo Nacional de Humanidades, Ciencias y Tecnologías (México)European CommissionMinisterio de Ciencia, Innovación y Universidades (España)Agencia Estatal de Investigación (España)Navarro Crespo, Rodrigo [0000-0001-6592-9871]Marcos-Fernández, Ángel [0000-0001-9004-9868]Caputto, María Dolores de Dios [0000-0002-5395-5834]Báez-García, José Eduardo [0000-0002-5738-4346]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2025202520252025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/382536reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-147542OB-I00The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI https://doi.org/10.3390/polym17050668https://doi.org/10.3390/polym17050668Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3825362026-05-22T06:33:51Z
dc.title.none.fl_str_mv Experimental Design (2⁴) to Improve the Reaction Conditions of Non-Segmented Poly(ester-urethanes) (PEUs) Derived from α,ω-Hydroxy Telechelic Poly(ε-caprolactone) (HOPCLOH)
title Experimental Design (2⁴) to Improve the Reaction Conditions of Non-Segmented Poly(ester-urethanes) (PEUs) Derived from α,ω-Hydroxy Telechelic Poly(ε-caprolactone) (HOPCLOH)
spellingShingle Experimental Design (2⁴) to Improve the Reaction Conditions of Non-Segmented Poly(ester-urethanes) (PEUs) Derived from α,ω-Hydroxy Telechelic Poly(ε-caprolactone) (HOPCLOH)
Maldonado-Estudillo, Jaime
Experimental design
Poly(ester-urethanes)
Number-average molecular weight
Poly(ε-caprolactone)
Telechelic
title_short Experimental Design (2⁴) to Improve the Reaction Conditions of Non-Segmented Poly(ester-urethanes) (PEUs) Derived from α,ω-Hydroxy Telechelic Poly(ε-caprolactone) (HOPCLOH)
title_full Experimental Design (2⁴) to Improve the Reaction Conditions of Non-Segmented Poly(ester-urethanes) (PEUs) Derived from α,ω-Hydroxy Telechelic Poly(ε-caprolactone) (HOPCLOH)
title_fullStr Experimental Design (2⁴) to Improve the Reaction Conditions of Non-Segmented Poly(ester-urethanes) (PEUs) Derived from α,ω-Hydroxy Telechelic Poly(ε-caprolactone) (HOPCLOH)
title_full_unstemmed Experimental Design (2⁴) to Improve the Reaction Conditions of Non-Segmented Poly(ester-urethanes) (PEUs) Derived from α,ω-Hydroxy Telechelic Poly(ε-caprolactone) (HOPCLOH)
title_sort Experimental Design (2⁴) to Improve the Reaction Conditions of Non-Segmented Poly(ester-urethanes) (PEUs) Derived from α,ω-Hydroxy Telechelic Poly(ε-caprolactone) (HOPCLOH)
dc.creator.none.fl_str_mv Maldonado-Estudillo, Jaime
Navarro Crespo, Rodrigo
Marcos-Fernández, Ángel
Dios Caputto, María Dolores de
Cruz-Jiménez, Gustavo
Báez-García, José Eduardo
author Maldonado-Estudillo, Jaime
author_facet Maldonado-Estudillo, Jaime
Navarro Crespo, Rodrigo
Marcos-Fernández, Ángel
Dios Caputto, María Dolores de
Cruz-Jiménez, Gustavo
Báez-García, José Eduardo
author_role author
author2 Navarro Crespo, Rodrigo
Marcos-Fernández, Ángel
Dios Caputto, María Dolores de
Cruz-Jiménez, Gustavo
Báez-García, José Eduardo
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Consejo Nacional de Humanidades, Ciencias y Tecnologías (México)
European Commission
Ministerio de Ciencia, Innovación y Universidades (España)
Agencia Estatal de Investigación (España)
Navarro Crespo, Rodrigo [0000-0001-6592-9871]
Marcos-Fernández, Ángel [0000-0001-9004-9868]
Caputto, María Dolores de Dios [0000-0002-5395-5834]
Báez-García, José Eduardo [0000-0002-5738-4346]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Experimental design
Poly(ester-urethanes)
Number-average molecular weight
Poly(ε-caprolactone)
Telechelic
topic Experimental design
Poly(ester-urethanes)
Number-average molecular weight
Poly(ε-caprolactone)
Telechelic
description Aliphatic unsegmented polyurethanes (PUs) have garnered relatively limited attention in the literature, despite their valuable properties such as UV resistance and biocompatibility, making them suitable for biomedical applications. This study focuses on synthesizing poly(ester-urethanes) (PEUs) using 1,6-hexamethylene diisocyanate and the macrodiol α,ω-hydroxy telechelic poly(ε-caprolactone) (HOPCLOH). To optimize the synthesis, a statistical experimental design approach was employed, a methodology not commonly utilized in polymer science. The influence of reaction temperature, time, reagent concentrations, and solvent type on the resulting PEUs was investigated. Characterization techniques included FT-IR, <sup>1</sup>H NMR, differential scanning calorimetry (DSC), gel permeation chromatography (GPC), optical microscopy, and mechanical testing. The results demonstrated that all factors significantly impacted the number-average molecular weight (<i>M</i><sub>n</sub>) as determined by GPC. Furthermore, the statistical design revealed crucial interaction effects between factors, such as a dependence between reaction time and temperature. For example, a fixed reaction time of 1 h, with the temperature varying from 50 °C to 61° C, did not significantly alter <i>M</i><sub>n</sub>. Better reaction conditions yielded high <i>M</i><sub>n</sub> (average: 162,000 g/mol), desirable mechanical properties (elongation at break > 1000%), low levels of unreacted HOPCLOH in the PEU films (OH/ESTER response = 0.0008), and reduced crystallinity (Δ<i>H</i><sub>m</sub> = 11 J/g) in the soft segment, as observed by DSC and optical microscopy. In contrast, suboptimal conditions resulted in low <i>M</i><sub>n</sub>, brittle materials with unmeasurable mechanical properties, high crystallinity, and significant amounts of residual HOPCLOH. The best experimental conditions were 61 °C, 0.176 molal, 8 h, and chloroform as the solvent (ε = 4.8).
publishDate 2025
dc.date.none.fl_str_mv 2025
2025
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/382536
url http://hdl.handle.net/10261/382536
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-147542OB-I00
The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI https://doi.org/10.3390/polym17050668
https://doi.org/10.3390/polym17050668
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Multidisciplinary Digital Publishing Institute
publisher.none.fl_str_mv Multidisciplinary Digital Publishing Institute
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
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repository.mail.fl_str_mv
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