Biodegradable Poly(ester–urethane–amide)s Based on Poly(ε-caprolactone) and Diamide–Diol Chain Extenders with Crystalline Hard Segments. Synthesis and Characterization
Abstract
Twenty seven poly(ester–urethane–amide)s (PEUAs) were synthesized from the reaction of α,ω-telechelic poly(ε-caprolactone) diols, 1,6-hexamethylene diisocyanate, and three different diamide–diol chain extenders derived from ε-caprolactone and three aliphatic diamines with increasing length ( n = 2, 4, and 6). The hard segment (HS) was designed to be crystalline and to introduce amide groups, more susceptible to hydrolysis than urethane or urea groups. Crystallization of the HS was achieved even at very low HS content, leading to a phase-separated material. Furthermore, HS crystallinity recovered from the material homogeneous melt on cooling. Thermal degradation was well above HS melting point, allowing for melt processing of these materials. HS melting point was affected by HS content, poly(ε-caprolactone) diol length, and chain extender length. The length scale of the phase-separated morphology lied in between 11 and 13 nm up to ∼60% HS content and decreased at higher HS content values. HS content was the main parameter affecting the mechanical properties. The prepared PEUAs degraded hydrolytically at very long times by surface erosion.
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The degree of crystallinity (Xc) of the tri-block copolymers was estimated using a melting enthalpy of 100% crystalline PLLA of about 93 KJ/mol and of PCL of 148 KJ/mol.
“The degree of crystallinity (X c ) has been estimated considering the value of the melting enthalpy of 100 % crystalline PLLA around 93 KJ/mol 25 while for the PCL a value of 148 KJ/mol 26 is considered.”
Cites
Crescenzi, V., Manzini, G., Calzolari, G., & Borri, C. (1972) · European Polymer Journal · doi:10.1016/0014-3057(72)90109-7 · Cited by 751 · see citing works
Szycher's Handbook of Polyurethanes
Ph.D, M. S. (1999) · CRC Press eBooks · doi:10.1201/9781482273984 · Cited by 506 · see citing works
Thermal degradation of segmented polyurethanes
Petrović, Z. S., Zavargo, Z., Flyn, J. H., & Macknight, W. J. (1994) · Journal of Applied Polymer Science · doi:10.1002/app.1994.070510615 · Cited by 404 · see citing works
Tatai, L., Moore, T., Adhikari, R., Malherbe, F., Jayasekara, R., Griffiths, I., & Gunatillake, P. A. (2007) · Biomaterials · doi:10.1016/j.biomaterials.2007.08.035 · Cited by 267 · see citing works
Cervantes‐Uc, J. M., Moo-Espinosa, J., Cauich-Rodríguez, J. V., Ávila‐Ortega, A., Vázquez‐Torres, H., Marcos-Fernández, Á. A., & Román, J. S. (2009) · Polymer Degradation and Stability · doi:10.1016/j.polymdegradstab.2009.06.022 · Cited by 181 · see citing works
Self-citationSkarja, G. A., & Woodhouse, K. A. (1998) · Journal of Biomaterials Science, Polymer Edition · doi:10.1163/156856298x00659 · Cited by 173 · see citing works
Górna, K., & Gogolewski, S. (2002) · Polymer Degradation and Stability · doi:10.1016/s0141-3910(01)00210-5 · Cited by 157 · see citing works
Marcos-Fernández, Á. A., Abraham, G. A., Valentin, J. L., et al. (2005) · Polymer · doi:10.1016/j.polymer.2005.12.007 · Cited by 150 · see citing works
Self-citationFernández–d’Arlas, B., Rueda, L., de la Caba, K., Mondragòn, I., & Eceiza, A. (2008) · Polymer Engineering and Science · doi:10.1002/pen.20983 · Cited by 130 · see citing works
Synthesis, Biodegradability, and Biocompatibility of Lysine Diisocyanate–Glucose Polymers
Zhang, J.-Y., Beckman, E. J., Hu, J., Yang, G.-G., Agarwal, S., & Hollinger, J. O. (2002) · Tissue Engineering · doi:10.1089/10763270260424132 · Cited by 115 · see citing works
Ding, M., Li, J., Fu, X., Zhou, J., Tan, H. S., Gu, Q., & Fu, Q. (2009) · Biomacromolecules · doi:10.1021/bm9006826 · Cited by 104 · see citing works
Bogdanov, B. G., Toncheva, V. D., Schacht, E. H., et al. (1999) · Polymer · doi:10.1016/s0032-3861(98)00552-7 · Cited by 97 · see citing works
Hassan, M. K., Mauritz, K. A., Storey, R. F., & Wiggins, J. S. (2006) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.21373 · Cited by 92 · see citing works
Furukawa, M., Mitsui, Y., Fukumaru, T., et al. (2005) · Polymer · doi:10.1016/j.polymer.2005.09.009 · Cited by 88 · see citing works
Caracciolo, P. C., Buffa, F., & Abraham, G. A. (2008) · Journal of Materials Science Materials in Medicine · doi:10.1007/s10856-008-3561-8 · Cited by 78 · see citing works
Graft copolymers of polyethylene by atom transfer radical polymerization
Matyjaszewski, K. A., Teodorescu, M., Miller, P. J., & Peterson, M. L. (2000) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/1099-0518(20000701)38:13 · Cited by 69 · see citing works
Hydrolytic degradation of PCL/PEO copolymers in alkaline media
Li, S., Chen, X. H., Gross, R. A., & McCarthy, S. P. (2000) · Journal of Materials Science Materials in Medicine · doi:10.1023/a:1008920326988 · Cited by 63 · see citing works
Abraham, G. A., Marcos-Fernández, Á. A., & Román, J. S. (2005) · Journal of Biomedical Materials Research Part A · doi:10.1002/jbm.a.30540 · Cited by 52 · see citing works
Self-citationIncorporation of different crystallizable amide blocks in segmented poly(ester amide)s
Lips, P. A. M., Broos, R., van Heeringen, M. J. M., et al. (2005) · Polymer · doi:10.1016/j.polymer.2005.07.009 · Cited by 47 · see citing works
Structure‐property relationship of L ‐tyrosine‐based polyurethanes for biomaterial applications
Sarkar, D., Yang, J., & Lopina, S. T. (2008) · Journal of Applied Polymer Science · doi:10.1002/app.27637 · Cited by 46 · see citing works
Caracciolo, P. C., de Queiroz, A. A. A., Higa, O. Z., et al. (2008) · Acta Biomaterialia · doi:10.1016/j.actbio.2008.02.016 · Cited by 45 · see citing works
Báez, J. E., Marcos-Fernández, Á. A., Lebrón‐Aguilar, R., & Martínez‐Richa, A. (2006) · Polymer · doi:10.1016/j.polymer.2006.10.023 · Cited by 39 · see citing works
Self-citationLips, P. A. M., van Luyn, M. J. A., Chiellini, E., et al. (2005) · Journal of Biomedical Materials Research Part A · doi:10.1002/jbm.a.30530 · Cited by 33 · see citing works
Synthesis and characterization of aliphatic poly(esteramide)s containing symmetrical bisamide blocks
Stapert, H. R., Dijkstra, P. J., & Feijén, J. (1998) · Macromolecular Symposia · doi:10.1002/masy.19981300109 · Cited by 32 · see citing works
Katayama, S., Murakami, T., Takahashi, Y., et al. (1976) · Journal of Applied Polymer Science · doi:10.1002/app.1976.070200411 · Cited by 26 · see citing works
Seawater degradable thermoplastic polyurethanes
Moravek, S. J., Hassan, M. K., Drake, D. J., et al. (2009) · Journal of Applied Polymer Science · doi:10.1002/app.31343 · Cited by 25 · see citing works
On the Effect of Alkyl End Group in Poly(ϵ-caprolactone) Oligomers: Preparation and Characterization
Báez, J. E., Marcos-Fernández, Á. A., & Galindo‐Iranzo, P. (2011) · Polymer-Plastics Technology and Engineering · doi:10.1080/03602559.2011.551976 · Cited by 15 · see citing works
Self-citationPolyurethane scaffolds as meniscus reconstruction materials
Heijkants, R. G. J. C. (2004) · University of Groningen research database (University of Groningen / Centre for Information Technology) · Cited by 11 · see citing works
Katayama, S., Horikawa, H., Ito, Y., et al. (1971) · Journal of Applied Polymer Science · doi:10.1002/app.1971.070150402 · Cited by 10 · see citing works
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Navarro-Baena, I., Marcos-Fernández, A., Fernández-Torres, A., Kenny, J. M., & Peponi, L. (2014) · RSC Advances · doi:10.1039/c3ra44786c · Cited by 43 · see citing works
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- Authors
- Báez, J. E., Ramírez, D., Valentín, J. L., & Marcos-Fernández, Á.
- Affiliations
- Consejo Superior de Investigaciones Científicas (ES)
- Instituto de Ciencia y Tecnología de Polímeros (CSIC), C/Juan de la Cierva 3, 28006 Madrid, Spain
- Corresponding author
- Marcos-Fernández, Ángel
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-08-16
- Volume
- 45
- Issue
- 17
- Pages
- 6966-6980
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2322862604
- Cited by
- 46
- References
- 29
- Citations by year
- 2026: 5 · 2025: 6 · 2024: 6 · 2023: 1 · 2022: 3 · 2021: 2 · 2020: 1 · 2019: 4 · 2018: 2 · 2017: 7 · 2016: 2 · 2015: 2 · 2014: 5
- FWCI
- 0.91
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer composites and self-healing
- Keywords
- polycaprolactone, hexamethylene diisocyanate, phase separation, thermal degradation, melt processing, hydrolytic degradation, surface erosion, mechanical properties, biodegradable polymers
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