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Study on the effect of linear alkyl [CH2CH2]m and ether [CH2CH2O]m groups in the α,ω-hydroxy telechelic poly(L-lactide) (HOPLLAOH) and their poly(ester-urethanes) (PEUs). Synthesis and Characterization

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Abstract

α,ω-Hydroxy telechelic poly(L-lactides) (HOPLLAOH) were synthesized by ring-opening polymerization of the L-lactide (L-LA) catalyzed by tin octoate [Sn(Oct)2] in the presence of two different types of initiators such as alkyl diols [HO−(CH2−CH2)m−OH] and ether diols [HO−(CH2−CH2−O)m−H] (where m = 2, 3, 4, 5, 6, and 8), and eventually, two different families of HOPLLAOH where the alkyl group (AG) [HO−PLLA−(CH2−CH2)m−PLLA−OH (HOPLLAaOH)] and ether group (EG) [HO−PLLA−(CH2−CH2−O)m−PLLA−OH (HOPLLAeOH)] are part of the backbone of the polymer with a systematic increase in these segments were synthesized. The number average molecular weight (M n) for all samples were similar [M n(NMR) = 1610–1980]. The weight percent (wt.%) of AG and EG had a dramatic effect on the glass transition temperature (T g) of HOPLLAaOH (from 19 to 3 °C) and HOPLLAeOH (from 19 to −1 °C), respectively, where the wt.% of AG or EG induced a decrease on the T g with a relationship that was inversely proportional. For poly(ester-urethanes) (PEUs) derived from HOPLLAaOH (PEUa) and HOPLLAeOH (PEUe) and 1,6-hexamethylene diisocyanate (HDI) showed an increase in the values of T g attributed to the hydrogen bonding of the urethanes groups in the main chain, for example from 19 (HOPLLA4aOH) to 39 °C (PEU4a) where 4a is indicating four aliphatic methylenes. However, the systematic variation in the repetitive unit from AG and EG in the PEUa and PEUe, respectively, it had also the similar effect on the T g, decreasing the values, for example, PEUa from 39 to 19 °C and PEUe from 39 to 17 °C, consistently as such as the previous HOPLLAOH species.

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Acknowledgements

José E. Báez thanks the “Programa para el Desarrollo Profesional Docente (PRODEP, Protocolo 166155)”, Dirección de Apoyo a la Investigación y al Posgrado (DAIP) at University of Guanajuato (UG), and “Sistema Nacional de Investigadores (SNI)” in México for financial support of the work. José E. Báez also thanks to Ángel Marcos-Fernández for believing in these ideas and providing financial support for the reagents. José E. Báez also thanks to the UG for the recent opportunity to work as an Assistant Professor. Marvin was used for drawing, displaying, and characterizing chemical structures, substructures, and reactions (Marvin Sketch 6.1.3, 2013, ChemAxon; http://www.chemaxon.com); a free software program with an academic license was provided by ChemAxon. Ángel Marcos-Fernández would like to thank the Ministry of Economy and Competitiveness (MINECO) for the financial support of this work within the framework of the Plan Nacional de I + D + I through the research project MAT2014-52644-R. Finally, José E. Báez thanks to Gema Reina Mendieta and David Gómez Varga for the acquisition of the NMR spectra and SEM micrographs, respectively.

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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

  3. Laboratory of Characterization of Polymers, Institute of Polymer Science and Technology, CSIC, C/Juan de la Cierva, 28006, Madrid, Spain

    Carolina García

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  1. José E. Báez
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Correspondence to José E. Báez.

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Báez, J.E., Marcos-Fernández, Á., Navarro, R. et al. Study on the effect of linear alkyl [CH2CH2]m and ether [CH2CH2O]m groups in the α,ω-hydroxy telechelic poly(L-lactide) (HOPLLAOH) and their poly(ester-urethanes) (PEUs). Synthesis and Characterization. J Polym Res 24, 199 (2017). https://doi.org/10.1007/s10965-017-1364-7

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