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Similarities between homopolymers and triblock copolymers derived from poly(ε-caprolactone) (PCL) macrodiols (HOPCL–E–PCLOH and HOPCL–PEG–PCLOH) and their poly(ester-ether-urethanes): synthesis and characterization

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Abstract

Ether group (E) diols [HO(CH2CH2O)xH, x = 2, 3, 4, 5, 6, and 8] and polyethylene glycol (PEG) [HO(CH2CH2O)xOH] were used as initiators in the ring-opening polymerization (ROP) of ε-caprolactone (CL) catalyzed by ammonium decamolybdate to synthesize the poly(ε-caprolactone) (PCL) macrodiols such as HOPCL–E–PCLOH and HOPCL–PEG–PCLOH, respectively. The effect of E or PEG on the crystallinity of the PCL segments (xPCL) in HOPCL–E–PCLOH homopolymer and HOPCL–PEG–PCLOH triblock copolymer was evidenced, respectively, where a weight percent of E or PEG was inversely proportional to the xPCL; this effect was explained due to that the ether segments are causing a partial disruption on the crystalline domain of PCL. A couple of species of poly(ester–ether–urethanes) (PEU) derived from HOPCL–E–PCLOH and HOPCL–PEG–PCLOH with 1,6-hexamethylene diisocyanate (HDI) were prepared, and these PEU showed an elastomeric behavior. Comparing two samples of PEU prepared from E (MW = 370 g/mol) (PEUE) and PEG (Mn = 408 g/mol) (PEUPEG), a parallel profile of their mechanical properties was seen. Eventually, HOPCL–E–PCLOH and HOPCL–PEG–PCLOH species showed similarities in terms of crystallinity and elastomeric behavior from their PEU derivatives. In addition, HOPCL–E–PCLOH and HOPCL–PEG–PCLOH and PEU samples were characterized by 1H NMR, FT-IR, GPC, DSC, and mechanical properties. Hence, homopolymers and triblock copolymers derived from PCL macrodiols with E or PEG segments, respectively, and their PEU had similarities in terms of chemical structure and physical properties

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Acknowledgements

José E. Báez would like to thank the “Consejo Nacional de Ciencia y Tecnología (CONACYT), Proyecto 284893”, “Dirección de Apoyo a la Investigación y al Posgrado (DAIP) at University of Guanajuato (UG), Proyecto CIIC 103/2018” and “Sistema Nacional de Investigadores (SNI)” in México for the financial support of the work. José E. Báez would also like to thank Ángel Marcos Fernández for believing in these ideas and providing financial support for the reagents through the project MAT2017-87204-R from the Ministry of Economy and Competitiveness (MINECO) of Spain. José E. Báez would like to thank Gema Reina Mendieta and Dr. Rebeca Yasmín Pérez Rodriguez for the acquisition of the NMR spectra and DSC instrument, respectively. Finally, José E. Báez would also like to thank Irene Caso and Sonoko Kawawada for her support.

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Authors and Affiliations

  1. Department of Chemistry, University of Guanajuato (UG), Noria Alta S/N, 36050, Guanajuato, GTO, Mexico

    José E. Báez

  2. Department of Polymer Physics, Elastomers and Applications Energy, Institute of Polymer Science and Technology, CSIC, C/Juan de la Cierva, 28006, Madrid, Spain

    Ángel Marcos-Fernández & Rodrigo Navarro

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  1. José E. Báez
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  2. Ángel Marcos-Fernández
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  3. Rodrigo Navarro
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Correspondence to José E. Báez.

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Báez, J.E., Marcos-Fernández, Á. & Navarro, R. Similarities between homopolymers and triblock copolymers derived from poly(ε-caprolactone) (PCL) macrodiols (HOPCL–E–PCLOH and HOPCL–PEG–PCLOH) and their poly(ester-ether-urethanes): synthesis and characterization. Chem. Pap. 73, 1287–1299 (2019). https://doi.org/10.1007/s11696-019-00683-3

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