Desarrollo de resinas híbridas poliuretano/acrílicas para la preparación de Scaffolds vía estereolitografía
La estereolitografía (SLA) es una técnica de impresión 3D de alta resolución, capaz de fabricar andamios con geometrías complejas para aplicaciones biomédicas. Estos andamios requieren propiedades químicas, mecánicas y estructurales adecuadas para la adhesión, proliferación y diferenciación celular,...
- Autores:
-
Cardona Cortés, Álvaro Antonio
- Tipo de recurso:
- Fecha de publicación:
- 2025
- Institución:
- Universidad de Antioquia
- Repositorio:
- Repositorio UdeA
- Idioma:
- spa
- OAI Identifier:
- oai:bibliotecadigital.udea.edu.co:10495/46141
- Acceso en línea:
- https://hdl.handle.net/10495/46141
- Palabra clave:
- Impresión 3D
Three-dimensional printing
Resinas acrílicas
Acrylic resins
Espectroscopia infrarroja por transformada de Fourier
Fourier transform infrared spectroscopy
Materiales - Propiedades mecánicas
Materials - Mechanical properties
Fotopolimerización
Photopolymerization
Ingeniería de tejidos
Tissue engineering
Estereolitografía
Stereolithography
Andamios del tejido
Tissue scaffolds
Materiales biocompatibles
Biocompatible materials
Poliuretano
Polyurethane
http://aims.fao.org/aos/agrovoc/c_28513
http://id.loc.gov/authorities/subjects/sh2009006799
http://id.loc.gov/authorities/subjects/sh85000675
http://id.loc.gov/authorities/subjects/sh88002426
http://id.loc.gov/authorities/subjects/sh2007002252
http://id.loc.gov/authorities/subjects/sh97005795
http://id.loc.gov/authorities/subjects/sh2003001133
https://id.nlm.nih.gov/mesh/D000076227
https://id.nlm.nih.gov/mesh/D054457
https://id.nlm.nih.gov/mesh/D001672
ODS 3: Salud y bienestar. Garantizar una vida sana y promover el bienestar de todos a todas las edades
ODS 9: Industria, innovación e infraestructura. Construir infraestructuras resilientes, promover la industrialización inclusiva y sostenible y fomentar la innovación
- Rights
- openAccess
- License
- http://creativecommons.org/licenses/by-nc-sa/4.0/
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| dc.title.spa.fl_str_mv |
Desarrollo de resinas híbridas poliuretano/acrílicas para la preparación de Scaffolds vía estereolitografía |
| title |
Desarrollo de resinas híbridas poliuretano/acrílicas para la preparación de Scaffolds vía estereolitografía |
| spellingShingle |
Desarrollo de resinas híbridas poliuretano/acrílicas para la preparación de Scaffolds vía estereolitografía Impresión 3D Three-dimensional printing Resinas acrílicas Acrylic resins Espectroscopia infrarroja por transformada de Fourier Fourier transform infrared spectroscopy Materiales - Propiedades mecánicas Materials - Mechanical properties Fotopolimerización Photopolymerization Ingeniería de tejidos Tissue engineering Estereolitografía Stereolithography Andamios del tejido Tissue scaffolds Materiales biocompatibles Biocompatible materials Poliuretano Polyurethane http://aims.fao.org/aos/agrovoc/c_28513 http://id.loc.gov/authorities/subjects/sh2009006799 http://id.loc.gov/authorities/subjects/sh85000675 http://id.loc.gov/authorities/subjects/sh88002426 http://id.loc.gov/authorities/subjects/sh2007002252 http://id.loc.gov/authorities/subjects/sh97005795 http://id.loc.gov/authorities/subjects/sh2003001133 https://id.nlm.nih.gov/mesh/D000076227 https://id.nlm.nih.gov/mesh/D054457 https://id.nlm.nih.gov/mesh/D001672 ODS 3: Salud y bienestar. Garantizar una vida sana y promover el bienestar de todos a todas las edades ODS 9: Industria, innovación e infraestructura. Construir infraestructuras resilientes, promover la industrialización inclusiva y sostenible y fomentar la innovación |
| title_short |
Desarrollo de resinas híbridas poliuretano/acrílicas para la preparación de Scaffolds vía estereolitografía |
| title_full |
Desarrollo de resinas híbridas poliuretano/acrílicas para la preparación de Scaffolds vía estereolitografía |
| title_fullStr |
Desarrollo de resinas híbridas poliuretano/acrílicas para la preparación de Scaffolds vía estereolitografía |
| title_full_unstemmed |
Desarrollo de resinas híbridas poliuretano/acrílicas para la preparación de Scaffolds vía estereolitografía |
| title_sort |
Desarrollo de resinas híbridas poliuretano/acrílicas para la preparación de Scaffolds vía estereolitografía |
| dc.creator.fl_str_mv |
Cardona Cortés, Álvaro Antonio |
| dc.contributor.advisor.none.fl_str_mv |
Giraldo Cortés, Luis Fernando Orozco López, Víctor Hugo |
| dc.contributor.author.none.fl_str_mv |
Cardona Cortés, Álvaro Antonio |
| dc.contributor.researchgroup.none.fl_str_mv |
Laboratorio de Investigación en Polímeros |
| dc.contributor.jury.none.fl_str_mv |
Martín Martínez, José Miguel Monsalve Carmona, Yuliana |
| dc.subject.lcsh.none.fl_str_mv |
Impresión 3D Three-dimensional printing Resinas acrílicas Acrylic resins Espectroscopia infrarroja por transformada de Fourier Fourier transform infrared spectroscopy Materiales - Propiedades mecánicas Materials - Mechanical properties Fotopolimerización Photopolymerization Ingeniería de tejidos Tissue engineering |
| topic |
Impresión 3D Three-dimensional printing Resinas acrílicas Acrylic resins Espectroscopia infrarroja por transformada de Fourier Fourier transform infrared spectroscopy Materiales - Propiedades mecánicas Materials - Mechanical properties Fotopolimerización Photopolymerization Ingeniería de tejidos Tissue engineering Estereolitografía Stereolithography Andamios del tejido Tissue scaffolds Materiales biocompatibles Biocompatible materials Poliuretano Polyurethane http://aims.fao.org/aos/agrovoc/c_28513 http://id.loc.gov/authorities/subjects/sh2009006799 http://id.loc.gov/authorities/subjects/sh85000675 http://id.loc.gov/authorities/subjects/sh88002426 http://id.loc.gov/authorities/subjects/sh2007002252 http://id.loc.gov/authorities/subjects/sh97005795 http://id.loc.gov/authorities/subjects/sh2003001133 https://id.nlm.nih.gov/mesh/D000076227 https://id.nlm.nih.gov/mesh/D054457 https://id.nlm.nih.gov/mesh/D001672 ODS 3: Salud y bienestar. Garantizar una vida sana y promover el bienestar de todos a todas las edades ODS 9: Industria, innovación e infraestructura. Construir infraestructuras resilientes, promover la industrialización inclusiva y sostenible y fomentar la innovación |
| dc.subject.decs.none.fl_str_mv |
Estereolitografía Stereolithography Andamios del tejido Tissue scaffolds Materiales biocompatibles Biocompatible materials |
| dc.subject.agrovoc.none.fl_str_mv |
Poliuretano Polyurethane |
| dc.subject.agrovocuri.none.fl_str_mv |
http://aims.fao.org/aos/agrovoc/c_28513 |
| dc.subject.lcshuri.none.fl_str_mv |
http://id.loc.gov/authorities/subjects/sh2009006799 http://id.loc.gov/authorities/subjects/sh85000675 http://id.loc.gov/authorities/subjects/sh88002426 http://id.loc.gov/authorities/subjects/sh2007002252 http://id.loc.gov/authorities/subjects/sh97005795 http://id.loc.gov/authorities/subjects/sh2003001133 |
| dc.subject.meshuri.none.fl_str_mv |
https://id.nlm.nih.gov/mesh/D000076227 https://id.nlm.nih.gov/mesh/D054457 https://id.nlm.nih.gov/mesh/D001672 |
| dc.subject.ods.none.fl_str_mv |
ODS 3: Salud y bienestar. Garantizar una vida sana y promover el bienestar de todos a todas las edades ODS 9: Industria, innovación e infraestructura. Construir infraestructuras resilientes, promover la industrialización inclusiva y sostenible y fomentar la innovación |
| description |
La estereolitografía (SLA) es una técnica de impresión 3D de alta resolución, capaz de fabricar andamios con geometrías complejas para aplicaciones biomédicas. Estos andamios requieren propiedades químicas, mecánicas y estructurales adecuadas para la adhesión, proliferación y diferenciación celular, así como para el transporte de nutrientes y metabolitos. La SLA exige el uso de materiales poliméricos adecuados que faciliten el proceso de curado mediante fotopolimerización por radiación UV. Sin embargo, la disponibilidad limitada de resinas fotocurables de bajo peso molecular, junto con problemas como alta rigidez, hidrofobicidad y baja biocompatibilidad en las opciones comerciales, además de los desafíos asociados a la eliminación de monómeros residuales, hace necesario desarrollar nuevas resinas con mejor biocompatibilidad y una mayor capacidad de adhesión celular para su uso en la fabricación de andamios. En este trabajo, se sintetizaron resinas híbridas de poli(uretano/acrilato) con control sobre su masa molar para obtener una resina de baja viscosidad. El nuevo sistema híbrido se sintetizó en tres etapas: la primera consistió en la síntesis de dos prepolímeros de poliéster poliólico diferentes, poli(adipato de butileno) (PBA) y poli(adipato-co-maleato de butileno) (PBAM). En el segundo paso, se utilizó diisocianato de isoforona (IPDI) como monómero para obtener el poliuretano. Finalmente, se empleó metacrilato de hidroxietilo (HEMA) en una tercera etapa para incorporar grupos metacrílicos en los extremos de la cadena del poliuretano, indispensables para la reacción de fotocurado durante su uso en impresión 3D. Al controlar el peso molecular del poliéster, se obtuvieron poliuretanos con pesos moleculares entre 3,000 y 3,500 g/mol. Los polímeros finales obtenidos se formularon como componentes base en prototipos de resina para impresión 3D, que incluyeron monómeros reactivos como HEMA, dimetacrilato de trietilenglicol (TEGMA) y metacrilato de glicidilo de bisfenol A (Bis GMA), junto con un sistema de fotoiniciación basado en óxido de fosfina de fenil bis(2,4,6-trimetilbenzóil) (BAPO). Estas formulaciones fueron optimizadas mediante la evaluación de la cinética de curado, utilizando un dispositivo de luz LED personalizado y monitoreando la conversión a lo largo del tiempo mediante espectros de infrarrojo por transformada de Fourier (FTIR). |
| publishDate |
2025 |
| dc.date.accessioned.none.fl_str_mv |
2025-05-28T14:41:29Z |
| dc.date.issued.none.fl_str_mv |
2025 |
| dc.type.none.fl_str_mv |
Trabajo de grado - Maestría |
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http://purl.org/redcol/resource_type/TM |
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Text |
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info:eu-repo/semantics/masterThesis |
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info:eu-repo/semantics/draft |
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draft |
| dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/10495/46141 |
| url |
https://hdl.handle.net/10495/46141 |
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spa |
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Shalaby & S. Ulrich, Eds.; First). Taylor & Francis Group, LLC. Sideridou, I., Tserki, V., & Papanastasiou, G. (2002). Effect of chemical structure on degree of conversion in light-cured dimethacrylate-based dental resins. In Biomaterials (Vol. 23). Voet, V. S. D., Strating, T., Schnelting, G. H. M., Dijkstra, P., Tietema, M., Xu, J., Woortman, A. J. J., Loos, K., Jager, J., & Folkersma, R. (2018). Biobased Acrylate Photocurable Resin Formulation for Stereolithography 3D Printing. ACS Omega, 3(2), 1403–1408. https://doi.org/10.1021/acsomega.7b01648 Yilmaz, B., Al Rashid, A., Mou, Y. A., Evis, Z., & Koç, M. (2021). Bioprinting: A review of processes, materials and applications. In Bioprinting (Vol. 23). Elsevier B.V. https://doi.org/10.1016/j.bprint.2021.e00148 Young, R. J., & Lovell, P. A. (2011). Introduction to Polymers (Taylor & Francis Group, Ed.; 3rd ed.). CRC Press. Zakeri, S., Vippola, M., & Levänen, E. (2020). A comprehensive review of the photopolymerization of ceramic resins used in stereolithography. In Additive Manufacturing (Vol. 35). Elsevier B.V. https://doi.org/10.1016/j.addma.2020.101177 |
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111 páginas |
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Universidad de Antioquia |
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Maestría en Ciencias Químicas |
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Medellín, Colombia |
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Facultad de Ciencias Exactas y Naturales |
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Campus Medellín - Ciudad Universitaria |
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Universidad de Antioquia |
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Giraldo Cortés, Luis FernandoOrozco López, Víctor HugoCardona Cortés, Álvaro AntonioLaboratorio de Investigación en PolímerosMartín Martínez, José MiguelMonsalve Carmona, Yuliana2025-05-28T14:41:29Z2025https://hdl.handle.net/10495/46141La estereolitografía (SLA) es una técnica de impresión 3D de alta resolución, capaz de fabricar andamios con geometrías complejas para aplicaciones biomédicas. Estos andamios requieren propiedades químicas, mecánicas y estructurales adecuadas para la adhesión, proliferación y diferenciación celular, así como para el transporte de nutrientes y metabolitos. La SLA exige el uso de materiales poliméricos adecuados que faciliten el proceso de curado mediante fotopolimerización por radiación UV. Sin embargo, la disponibilidad limitada de resinas fotocurables de bajo peso molecular, junto con problemas como alta rigidez, hidrofobicidad y baja biocompatibilidad en las opciones comerciales, además de los desafíos asociados a la eliminación de monómeros residuales, hace necesario desarrollar nuevas resinas con mejor biocompatibilidad y una mayor capacidad de adhesión celular para su uso en la fabricación de andamios. En este trabajo, se sintetizaron resinas híbridas de poli(uretano/acrilato) con control sobre su masa molar para obtener una resina de baja viscosidad. El nuevo sistema híbrido se sintetizó en tres etapas: la primera consistió en la síntesis de dos prepolímeros de poliéster poliólico diferentes, poli(adipato de butileno) (PBA) y poli(adipato-co-maleato de butileno) (PBAM). En el segundo paso, se utilizó diisocianato de isoforona (IPDI) como monómero para obtener el poliuretano. Finalmente, se empleó metacrilato de hidroxietilo (HEMA) en una tercera etapa para incorporar grupos metacrílicos en los extremos de la cadena del poliuretano, indispensables para la reacción de fotocurado durante su uso en impresión 3D. Al controlar el peso molecular del poliéster, se obtuvieron poliuretanos con pesos moleculares entre 3,000 y 3,500 g/mol. Los polímeros finales obtenidos se formularon como componentes base en prototipos de resina para impresión 3D, que incluyeron monómeros reactivos como HEMA, dimetacrilato de trietilenglicol (TEGMA) y metacrilato de glicidilo de bisfenol A (Bis GMA), junto con un sistema de fotoiniciación basado en óxido de fosfina de fenil bis(2,4,6-trimetilbenzóil) (BAPO). Estas formulaciones fueron optimizadas mediante la evaluación de la cinética de curado, utilizando un dispositivo de luz LED personalizado y monitoreando la conversión a lo largo del tiempo mediante espectros de infrarrojo por transformada de Fourier (FTIR).Síntesis de polímerosCOL0167869MaestríaMagíster en Ciencias Químicas111 páginasapplication/pdfspaUniversidad de AntioquiaMaestría en Ciencias QuímicasMedellín, ColombiaFacultad de Ciencias Exactas y NaturalesCampus Medellín - Ciudad Universitariahttp://creativecommons.org/licenses/by-nc-sa/4.0/info:eu-repo/semantics/openAccessAttribution-NonCommercial-ShareAlike 4.0 Internationalhttp://purl.org/coar/access_right/c_abf2Impresión 3DThree-dimensional printingResinas acrílicasAcrylic resinsEspectroscopia infrarroja por transformada de FourierFourier transform infrared spectroscopyMateriales - Propiedades mecánicasMaterials - Mechanical propertiesFotopolimerizaciónPhotopolymerizationIngeniería de tejidosTissue engineeringEstereolitografíaStereolithographyAndamios del tejidoTissue scaffoldsMateriales biocompatiblesBiocompatible materialsPoliuretanoPolyurethanehttp://aims.fao.org/aos/agrovoc/c_28513http://id.loc.gov/authorities/subjects/sh2009006799http://id.loc.gov/authorities/subjects/sh85000675http://id.loc.gov/authorities/subjects/sh88002426http://id.loc.gov/authorities/subjects/sh2007002252http://id.loc.gov/authorities/subjects/sh97005795http://id.loc.gov/authorities/subjects/sh2003001133https://id.nlm.nih.gov/mesh/D000076227https://id.nlm.nih.gov/mesh/D054457https://id.nlm.nih.gov/mesh/D001672ODS 3: Salud y bienestar. Garantizar una vida sana y promover el bienestar de todos a todas las edadesODS 9: Industria, innovación e infraestructura. Construir infraestructuras resilientes, promover la industrialización inclusiva y sostenible y fomentar la innovaciónDesarrollo de resinas híbridas poliuretano/acrílicas para la preparación de Scaffolds vía estereolitografíaTrabajo de grado - Maestríahttp://purl.org/redcol/resource_type/TMTexthttp://purl.org/coar/version/c_b1a7d7d4d402bcceinfo:eu-repo/semantics/masterThesisinfo:eu-repo/semantics/draftAlqutaibi, A. Y., Alghauli, M. A., Aljohani, M. H. A., & Zafar, M. S. (2024). Advanced additive manufacturing in implant dentistry: 3D printing technologies, printable materials, current applications and future requirements. In Bioprinting (Vol. 42). Elsevier B.V. https://doi.org/10.1016/j.bprint.2024.e00356Anycubic. (2024, December 3). Anycubic Photon D2. https://www.anycubic.es/products/photon-d2ASTM International. (2022). 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In Advanced Drug Delivery Reviews (Vol. 59, Issues 4–5, pp. 249–262). https://doi.org/10.1016/j.addr.2007.03.015Coenen, A. M. J., Bernaerts, K. V., Harings, J. A. W., Jockenhoevel, S., & Ghazanfari, S. (2018). Elastic materials for tissue engineering applications: Natural, synthetic, and hybrid polymers. In Acta Biomaterialia (Vol. 79, pp. 60–82). Acta Materialia Inc. https://doi.org/10.1016/j.actbio.2018.08.027Cults. (2022, September 29). Generador de muestras de resistencia a la tracción ISO 527-2, ASTM D638-14. Cults. https://cults3d.com/es/modelo3d/variado/tensile-strength-test-specimen-generator-iso-527-2-astm-d638-14Diaz, A. (2022, March 28). UltiMakers’s Thingiverse. Open-Source Library of Tissue Engineering Scaffolds. https://www.thingiverse.com/thing:5333296/filesDizon, J. R. C., Espera, A. H., Chen, Q., & Advincula, R. C. (2018). Mechanical characterization of 3D-printed polymers. In Additive Manufacturing (Vol. 20, pp. 44–67). 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(2020). 3D scaffolding of fast photocurable polyurethane for soft tissue engineering by stereolithography: Influence of materials and geometry on growth of fibroblast cells. European Polymer Journal, 139. https://doi.org/10.1016/j.eurpolymj.2020.109988Fouassier, J. P., Allonas, X., Laleveé Jacques, & Dietlin, C. (2010). Photoinitiators for free radical polymerization reactions. In N. S. Allen (Ed.), Photochemistry and Photophysics of Polymer Materials (pp. 351–419). John Wiley & Sons, Inc.Green, A. (2010). Industrial Photoinitiators. A Technical Guide (CRC Press & Taylor & Francis Group, Eds.; 1st ed.). Taylor and Francis Group, LLC.Guelcher, S. A., Gallagher, K. M., Didier, J. E., Klinedinst, D. B., Doctor, J. S., Goldstein, A. S., Wilkes, G. L., Beckman, E. J., & Hollinger, J. O. (2005). Synthesis of biocompatible segmented polyurethanes from aliphatic diisocyanates and diurea diol chain extenders. Acta Biomaterialia, 1(4), 471– 484. https://doi.org/10.1016/j.actbio.2005.02.007Jeong, Y. G., Yoo, J. J., Lee, S. J., & Kim, M. S. (2024). 3D digital light process bioprinting: Cutting-edge platforms for resolution of organ fabrication. In Materials Today Bio (Vol. 29). Elsevier B.V. https://doi.org/10.1016/j.mtbio.2024.101284Kumar, R., Kumar, M., & Chohan, J. S. (2021). The role of additive manufacturing for biomedical applications: A critical review. In Journal of Manufacturing Processes (Vol. 64, pp. 828–850). Elsevier Ltd. https://doi.org/10.1016/j.jmapro.2021.02.022Kupka, V., Vojtova, L., Fohlerova, Z., & Jancar, J. (2016). Solvent free synthesis and structural evaluation of polyurethane films based on poly(Ethylene glycol) and poly(caprolactone). Express Polymer Letters, 10(6), 479–492. https://doi.org/10.3144/expresspolymlett.2016.46Lakkala, P., Munnangi, S. R., Bandari, S., & Repka, M. (2023). Additive manufacturing technologies with emphasis on stereolithography 3D printing in pharmaceutical and medical applications: A review. International Journal of Pharmaceutics: X, 5. https://doi.org/10.1016/j.ijpx.2023.100159Lalwani, C. (2021, January 29). LCD 3D Printing vs. FDM 3D Printing. Phrozen 3d. https://phrozen3d.com/blogs/resin-3d-printing-latest-news/lcd-3d-printing-vsfdm-3d-printingLang, M., Hirner, S., Wiesbrock, F., & Fuchs, P. (2022). A Review on Modeling Cure Kinetics and Mechanisms of Photopolymerization. Polymers, 14(10). https://doi.org/10.3390/polym14102074Ligon, S. C., Liska, R., Stampfl, J., Gurr, M., & Mülhaupt, R. (2017). Polymers for 3D Printing and Customized Additive Manufacturing. In Chemical Reviews (Vol. 117, Issue 15, pp. 10212–10290). American Chemical Society. https://doi.org/10.1021/acs.chemrev.7b00074Lin, H., Zhang, D., Alexander, P. G., Yang, G., Tan, J., Cheng, A. W. M., & Tuan, R. S. (2013). 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