Hydrolytic and enzymatic degradation of a poly(å-caprolactone) network

“NOTICE: this is the author’s version of a work that was accepted for publication in Polymer Degradation and Stability. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Polymer Degradation and Stability, [Volume 97, Issue 8, August 2012, Pages 1241–1248] DOI 10.1016/j.polymdegradstab.2012.05.038Long-term hydrolytic and enzymatic degradation profiles of poly(å-caprolactone) (PCL) networks were obtained. The hydrolytic degradation studies were performed in water and phosphate buffer solution (PBS) for 65 weeks. In this case, the degradation rate of PCL networks was faster than previous results in the literature on linear PCL, reaching a weight loss of around 20% in 60 weeks after immersing the samples either in water or in PBS conditions. The enzymatic degradation rate in Pseudomonas Lipase for 14 weeks was also studied, with the conclusion that the degradation profile of PCL networks is lower than for linear PCL, also reaching a 20% weight loss. The weight lost, degree of swelling, and calorimetric and mechanical properties were obtained as a function of degradation time. Furthermore, the morphological changes in the samples were studied carefully through electron microscopy and crystal size through X-ray diffraction. The changes in some properties over the degradation period such as crystallinity, crystal size and Young¿s modulus were smaller in the case of enzymatic studies, highlighting differences in the degradation mechanism in the two studies, hydrolytic and enzymatic.The authors would like to acknowledge the support of the Spanish Ministry of Science and Education through the DPI2010-20399-004-03 project. JM Meseguer-Duenas and A Vidaurre also would like to acknowledge the support of the CIBER-BBN, an initiative funded by the VI National R&D&i Plan 2008-2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions and financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund. The translation of this paper was funded by the Universidad Politecnica de Valencia, SpainCastilla Cortázar, MIC.; Más Estellés, J.; Meseguer Dueñas, JM.; Escobar Ivirico, JL.; Marí Soucase, B.; Vidaurre, A. (2012). Hydrolytic and enzymatic degradation of a poly(å-caprolactone) network. Polymer Degradation and Stability. 97(8):1241-1248. https://doi.org/10.1016/j.polymdegradstab.2012.05.038S1241124897

Molecular relaxation and ionic conductivity of ionic liquids confined in a poly(vinylidene fluoride) polymer matrix: Influence of anion and cation type

Blends of poly(vinylidene fluoride) (PVDF) and ionic liquids (ILs) with different cations and anions have been prepared by solvent casting. The IL content was the same in all blends of the series. Molecular relaxation and ionic conductivity have been systematically studied by broadband dielectric relaxation spectroscopy (BDS) in wide frequency (0.1 Hz-1 MHz) and temperature ranges (-120 to 150 degrees C) and the results have been analysed in terms of dielectric modulus M*(omega) and conductivity sigma*(omega) formalisms. The main relaxation process (beta-relaxation) of the amorphous phase of the blend that integrates amorphous polymer chain segments and IL molecules was observed. Significant differences in the Vogel-Fulcher-Tammann (VFT) fitting parameters in the PVDF/IL blends with different anions were detected. The conductivity sigma*(omega) formalism shows that it is strongly dependent on the miscibility of the IL with the amorphous PVDF chains and the type of anion. The Barton-Namikawa-Nakajima (BNN) relation sigma(0) similar to omega(c) is fulfilled for all PVDF/IL blends except for that containing 1-ethyl-3-methylimidazolium hydrogen sulfate, [Emim][HSO4]. The activation energy of the ac conductivity, calculated according to the Dyre model, decreases for all PVDF/IL blends with respect to neat PVDF. The structure of the cation of the IL has been found to exert less influence on the dielectric and conductivity properties of the blends.This work was supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UID/FIS/04650/2013 and the Associated Laboratory Research Unit for Green Chemistry, Technologies and Clean Processes, LAQV (financed by national funds from FCT/MEC, UID/QUI/50006/2013 and ERDF under the PT2020, POCI-01-0145-FEDER-007265). The authors thank FEDER funds through the COMPETE 2020 Programme and National Funds through FCT under the projects PTDC/CTM-ENE/5387/2014, PTDC/EEI-SII/5582/2014 and PTDC/FIS-MAC/28157/2017. D.M.C., C.M.C., J.M.S center dot S.E. and P.M.R. also thank to the FCT for grants SFRH/BPD/121526/2016 and SFRH/BPD/112547/2015, and Investigator FCT contracts IF/00355/2012 and IF/0621/2015, respectively. Financial support from the Spanish Ministry of Economy and Competitiveness (MINECO) through the project MAT2016-76039-C4-(1 and 3)-R (AEI/FEDER, UE) (including the FEDER financial support) and from the Basque Government Industry and Education Departments under the ELKARTEK, HAZITEK and PIBA (PIBA-2018-06) programs, respectively, are acknowledged. CIBER-BBN is an initiative funded by the VI National R&D&I Plan 2008-2011, Iniciativa Ingenio 2010, Consolider Program. CIBER Actions are financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund