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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Synthèse de nouveaux polyesters “verts” issus de ressources oléagineuses : application au renfort au choc du poly(L-lactide) / Synthesis of novel “green” polyesters from plant oils : application to the rubber-toughening of poly(L-lactide)

Lebarbe, Thomas 06 December 2013 (has links)
Dans cette étude, plusieurs voies ont été explorées dans l’objectif d’utiliser des polyesters aliphatiques issus de ressources oléagineuses comme additifs pour le renfort au choc du poly(L-lactide) (PLLA). Dans un premier temps, des poly(ester-amide)s (PEAs) ont été synthétisés à partir de dérivés de l’huile de ricin. La relation structure-propriétés des PEAs obtenus a été clairement établie. La dispersion des PEAs (à différents taux) par extrusion à l’état fondu dans une matrice de PLLA a ensuite été effectuée, démontrant un accroissement de la résilience de ces mélanges en comparaison au PLLA seul. Une étude systématique reliant la structure d’une large gamme de polyesters aux propriétés des mélanges polyesters/PLLA, a ensuite été réalisée. Une forte dépendance de la résilience des mélanges polyesters/PLLA avec la cristallinité de l’additif polyester a été observée et quantifiée.Une amélioration des propriétés mécaniques du PLLA a également été obtenue par polymérisation par ouverture de cycle du lactide amorcée par un poly(acide ricinoléique) di-hydroxy téléchélique. Les copolymères triblocs ainsi formés ont été caractérisés d’un point de vue morphologique et mécanique.Enfin, un travail exploratoire utilisant l’ADMET comme méthode de polymérisation a été conduit, permettant la synthèse de nouveaux polymères prometteurs pour le renfort au choc du PLLA. Notamment, la copolymérisation de α,ω-diènes bio-sourcés a permis de mimer le polyéthylène basse densité linéaire, couramment employé pour le renfort au choc du PLLA. / The objective of this thesis work, is to promote the use of fatty acid-based aliphatic polyesters as impact modifiers for poly(L-lactide) (PLLA).Firstly, poly(ester-amide)s (PEAs) have been synthesized from castor oil derivatives. The structure-properties relationship of the PEAs so-formed was clearly established. The PEAs were then melt-blended with PLLA by extrusion, yielding blends with improved impact strength compared to neat PLLA.A series of polyesters covering a wide range of thermo-mechanical properties was then employed to evaluate the influence of the polyester morphology on the properties of the blends with PLLA. A strong dependence of the impact strength of the blends was noticed with the crystallinity degree of the polyester additive.An improvement of the mechanical properties of PLLA was also obtained by ring-opening polymerization of lactide initiated by a di-hydroxy telechelic poly(ricinoleic acid). The so-formed triblock copolymers were fully characterized in terms of morphology and mechanical properties.Finally, an exploratory investigation related to the synthesis of PLLA impact modifiers by ADMET was carried out. Particularly, the copolymerization of two bio-based α,ω-dienes yielded a series of “LLDPE like” polyesters, LLDPE being a commonly used impact modifier for PLLA.
2

Izolace ligninu z hroznových semen a jeho aplikace jako plniva pro polyhydroxyalkanoáty (PHA) / Isolation of lignin from grape seeds and its application as filler for polyhydroxyalkanoates (PHA)

Vostrejš, Pavel January 2020 (has links)
This diploma thesis deals with 1) the preparation of biodegradable polymer films based on polyhydroxyalkanoates (PHA) and 2) their modification by lignin as an active additive. The motivation for this work was to prepare active packaging material for food packaging. Polymer films were prepared by blending of neat crystalline poly(3hydroxybutyrate) (P3HB) and amorphous polyhydroxyalkanoate (PHA). The lignin was isolated from grape seeds derived from grape pomace. The solubility of lignin in chloroform was improved by acetylation. The properties of the isolated lignin were determined by elemental analysis, ash content, and infrared spectroscopy (FTIR). Lignin was used as an active additive for the modification of polymeric films prepared by solution casting of P3HB or P3HB blended with amorphous polyhydroxyalkanoate. The effect of different concentrations of lignin in the range of 1 to 10 % was tested. The lignin type and concentration had a different influence on the final thermal and mechanical behaviour of polymeric films. Lignin increased the values of the Young modulus and tensile strength of the prepared films. Differential scanning calorimetry data confirmed that lignin positively modified crystallization kinetics of P3HB. Thermogravimetry was used to analyse the thermal stability of PHA films. Lignin markedly increased the thermal stability of PHA films. However, acetylated lignin harms the mechanical properties of films. Moreover, this work showed that lignin isolated from grape seeds and added into PHA films proved its high antioxidant capacity. PHA films with lignin displayed much better gas barrier properties compared with PHA films without lignin. The prepared bioactive PHA films fulfil the requirements for sustainable food packaging with high antioxidant capacity and excellent gas barrier properties.

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