Yes / In this work, effect of ultrasound on molecular structure development of Polylactide (PLA) was studied. It was found that the intrinsic viscosity of PLA decreased with increasing treating time, temperature and ultrasound time. Different from traditional thermal degradation of PLA, the degradation of PLA under ultrasound treatment showed that chain scission and chain combination of PLA competed with each other in the degradation process, which could be divided into two steps. The mechanism of ultrasound degradation of PLA was proposed. Furthermore, Thermal properties were characterized by DSC to show heat and ultrasound effects on molecular structure development of PLA.

Polylactide-siloxane triblock copolymers with pendent carboxylic acid functional groups have been designed and synthesized for study as magnetite nanoparticle dispersion stabilizers. Magnetic nanoparticles are of interest in a variety of biomedical applications, including magnetic field-directed drug delivery and magnetic cell separations. Small magnetite nanoparticles are desirable due to their established biocompatibility and superparamagnetic (lack of magnetic hysteresis) behavior. For in-vivo applications it is important that the magnetic material be coated with biocompatible organic materials to afford dispersion characteristics or to further modify the surfaces of the complexes with biospecific moieties. The synthesis of the triblock copolymers is comprised of three reactions. Difunctional, controlled molecular weight polymethylvinylsiloxane oligomers with either aminopropyl or hydroxybutyl endgroups were prepared in ring-opening redistribution reactions. These oligomers were utilized as macroinitiators for ring-opening L-lactide to provide triblock materials with polymethylvinylsiloxane central blocks and poly(L-lactide) endblocks. The molecular weights of the poly(L-lactide) endblocks were controlled by the mass of L-lactide relative to the moles of macroinitiator. The vinyl groups on the polysiloxane center block were further functionalized with carboxylic acid groups by adding mercaptoacetic acid across the pendent double bonds in an ene-thiol free radical reaction. The carboxylic acid functional siloxane central block was designed to bind to the surfaces of magnetite nanoparticles, while the poly(L-lactide)s served as tailblocks to provide dispersion stabilization in solvents for the poly(L-lactide). The copolymers were complexed with magnetite nanoparticles by electrostatic adsorption of the carboxylates onto the iron oxide surfaces and these complexes were dispersible in dichloromethane. The poly(L-lactide) tailblocks extended into the dichloromethane and provided steric repulsion between the magnetite-polymer complexes. / Master of Science

La compréhension de la relation structure-propriété est un élément indispensable pour la conception et l'amélioration des matériaux, notamment ceux utilisés dans le domaine de l'emballage alimentaire. Afin de contribuer à la compréhension des phénomènes de transport dans le polylactide (PLA), les travaux de ce mémoire se sont portés sur la modulation de la microstructure du PLA en lien avec ses propriétés barrière aux gaz (oxygène, hélium) et aux composés organiques (esters éthyliques, sondes fluorescentes). La microstructure a été modulée i) par l'ajout de plastifiant (ATBC, PEG), ii) par la cristallisation selon trois procédés, le traitement thermique, la cristallisation induite par des composés organiques et le biétirage. Ces approches ont permis, respectivement, de faire varier le pourcentage de phase amorphe par rapport à la phase cristalline, la fraction de volume libre au sein de la phase amorphe, et la structure cristalline. L'augmentation de la cristallinité par recuit à partir du vitreux n'a pas conduit à une diminution systématique et importante des coefficients de transport des molécules de gaz (oxygène, hélium). Deux hypothèses principales ont ainsi été formulées pour expliquer ce comportement : la dédensification de la phase amorphe et la présence d'une phase amorphe mobile et d'une phase rigide. L'influence du biétirage sur les propriétés barrière aux gaz a été très limitée même au plus fort ratio d'étirage (4×4). Néanmoins cette technique a l'avantage de pouvoir réaliser des morphologies différentes.L'étude des coefficients de transport par plusieurs méthodes (sorption, perméation, diffusion par contact solide/solide) a mis en évidence la loi d'échelle ( ) dans le cas des molécules fluorescentes et a permis une première estimation du coefficient alpha. Une approche par Résonance Paramagnétique Electronique a permis de mettre en évidence des séparations de phase des systèmes plastifiés par ATBC et PEG. Cette méthode pourrait constituer un des moyens de sonder les hétérogénéités locales et les changements microstructuraux liés à l'interaction de molécules perméantes et de la matrice polymère, lors du transport. / The understanding of the relationship between structure and properties is fundamental for materials conception and improvement, in particular for those used in food packaging industry. To contribute to the understanding of the transport phenomena in polylactide (PLA), this study was focused on the adjustment of PLA microstructure modulation related to its gas (oxygen, helium) and organic compounds (ethyl esters, fluorescent molecules) barrier properties. The microstructure was modulated i) by adding plasticizers (ATBC, PEG), ii) by crystallizing according to 3 processes, thermal treatment, organic compounds induced crystallization and biaxially orientation. These approaches, respectively enabled to vary, the ratio of amorphous phase and crystalline phase, free volume fraction into amorphous phase and the crystalline structure. The increase in crystallinity degree, by annealing from cold state, did not result in a systematic and significant decrease of the gas molecules transport coefficient (oxygen, helium). Two main hypotheses were formulated to explain this behaviour: de-densification of amorphous phase and the presence of a mobile and a rigid amorphous phase. The influence of biaxially orientation on gas barrier properties was strongly limited even at the highest stretching ratio (4×4). Nevertheless several morphologies can be formed thanks to this technique.The transport coefficient study by several methods (sorption, permeation and diffusion by solid/solid contact) highlighted a scale law with the fluorescent molecules and allowed to a first estimation of the α coefficient. Thanks to Electronic Spin Resonance approach, phase separation of plasticized systems by ATBC and PEG were highlighted. This method could be one of the means to probe the local heterogeneities and the micro-structural changes related to the interaction of permeating molecules and polymer matrix during transport.

Des nanocapsules (NCs) biodégradables contenant une substance active et destinées à des applications environnementales ont été élaborées par un procédé d’émulsion-évaporation de solvant couplé à une réaction de chimie « click » interfaciale. Deux types de réactions « click » ont été testés: (i) cycloaddition azide-alcyne catalysée par le Cu(I) et (ii) thiol-ène. Ces NCs sont constituées d’une écorce en polymère hydrophobe (polylactide) entourant un cœur liquide (Miglyol®810) et recouverte d’une couronne hydrophile polysaccharide (dextrane). Des nanosphères (sans cœur liquide) ont aussi été produites. Ces nano-objets ont été caractérisés en termes de distribution de tailles, morphologie, taux et épaisseur de recouvrement en dextrane ainsi qu’efficacité de couplage « click ». La stabilité colloïdale en milieu salin et la stabilité du recouvrement en présence d’un tensioactif compétitif ont été étudiées. Enfin, une substance active a été encapsulée et libérée à partir des nano-objets / Biodegradable nanocapsules allowing encapsulation of active substances for environmental applications were produced by emulsion-evaporation method combined with a “click” reaction occurring at the liquid/liquid interface of emulsion droplets. Two types of “click” reaction were tested: (i) copper-catalyzed azide-alkyne cycloaddition (CuAAC) and (ii) thiol-ene reaction. The NCs are composed of a hydrophobic polymer shell (polylactide), a liquid core (Miglyol®810) and a hydrophilic polysaccharide coating (dextran). For comparison, nanospheres (without oily core) were also prepared. These nano-objects were characterized in terms of size distribution, dextran coverage density and thickness, “click” coupling efficiency and morphology. Colloidal stability in NaCl solutions as well as dextran coverage stability against an anionic competitive surfactant were also studied. Finally, an active substance was encapsulated and released from these nano-objects

Ces dernières années, une attention particulière a été portée aux polymères biodégradables et biocompatibles, notamment du point de vue écologique. Le développement de biopolymères pour des applications d'emballage alimentaire implique des exigences industrielles spécifiques telles qu’un bas prix ainsi que de bonnes propriétés mécaniques, thermiques et barrières. Le Polylactide (PLA) a attiré beaucoup d’attention car il est produit à partir de ressources naturelles renouvelables, et en raison de sa capacité de mise en œuvre et de ses bonnes propriétés mécaniques. Pour que le PLA puisse être développé à grande échelle pour des applications industrielles dans le domaine de l’emballage, ses propriétés barrières doivent être améliorées. La cristallisation est une méthode très utilisée pour améliorer les propriétés barrières mais n'est pas suffisante dans le cas du PLA. De nouvelles stratégies sont étudiées pour obtenir des effets plus importants. L'une d'entre elles consiste à confiner géométriquement le polymère jusqu’à l’échelle nano en utilisant le procédé de co-extrusion multicouche combiné éventuellement avec un recuit. Cette technologie respecte l'environnement et a déjà prouvé son efficacité pour améliorer les propriétés barrières aux gaz dans le cas d'autres polymères.Cette étude propose d'abord le développement de films PLA avec des structures cristallines différentes dans le but d'optimiser les conditions de cristallisation pour obtenir de meilleures propriétés barrières à l'oxygène. Parmi les différentes structures cristallines obtenues, la perméabilité est la meilleure lorsque le PLA a été cristallisé rapidement à partir de l’état vitreux pour atteindre un degré de cristallinité élevé et un bon découplage de la phase amorphe et cristalline. Ensuite, le PLLA a été confiné par deux polymères amorphes, le Polystyrène et le Polycarbonate. Nous avons montré que le polymère confineur peut influencer la structure cristalline et la mobilité de la phase amorphe du PLLA, influençant ainsi sa perméabilité. / In recent years, much attention has been focused on biodegradable and biocompatible polymers, particularly from an ecological viewpoint. The development of biopolymers for food-packaging applications implies ecofriendly character to specific industrial requirements as low-cost and good mechanical, thermal and barrier properties. Polylactide (PLA) has been attracting great attention, because it can be obtained from renewable sources, and due to its good process ability and mechanical properties. As one of the major challenges for high performance PLA packaging at a large scale is the improvement of its gas barrier properties, the tailoring of the PLA microstructure. Crystallization is a method used to improve barrier properties but is not sufficient in the case of PLA. New strategies are actually studied to obtained stronger effects. One of them consists in the geometrical confinement of the polymer at the molecular scale using the layer-multiplying co-extrusion process combined eventually with annealing processes to create nanometric thickness layers.This technology is environmentally friendly and has already proved its efficiency to improve the gas barrier properties in case of other polymers. This study first proposes the development of PLA films with different structures crystalline with the aim of optimize the crystallization conditions to get better oxygen barrier properties. Among the different crystalline structures obtained, permeability was better when PLA was rapidly crystallized from glass to reach a high crystallinity degree and decoupling of the amorphous and crystalline phase. Then, PLLA was confined by two amorphous polymers, polystyrene and polycarbonate, and its crystals structure and amorphous mobility was changed. We showed that the confiner polymer could influence PLLA confinement, both in the crystalline phase and in the amorphous phase, thus influencing its permeability.

Polylactide (PLA) is a biodegradable and biocompatible alternative to traditional petrochemicalbased polymers. Synthesised by the ring-opening polymerisation of lactide (LA), the dehydrated form of lactic acid, PLA sits within a renewable cycle, and can be used in many commodity and biomedical applications. The intrinsic stereochemistry of LA can lead to a variety of polymer microstructures, and current industrially used initiators allow no control over this. Within this thesis a series of investigations into the use of amine tris(phenolate) metal complexes as stereoselective initiators for the ROP of LA are discussed. Chapter 1 introduces the field of ring-opening polymerisation (ROP) via a coordination insertion mechanism, presents previously reported initiators, and examines the influence of stereocomplexation on the physical properties of PLA chains. This introductory chapter also includes an in-depth review of recent developments in poly(phenolate) complexes of Group 4 and rare earth metals. Chapter 2 describes the synthesis of a series of isopropoxide and zwitterionic Group 4 complexes featuring the amine tris(phenolate) ligand motif, with emphasis on the effect of ligand variation on complex structure. The potential of the resulting complexes as initiators for the ROP of LA is also investigated, with in depth kinetic studies allowing for a proposed diastereoselective mechanism of stereocontrol. Chapter 3 details the synthesis of a series of borohydride and amide Group 4 amine tris(phenolate) complexes, and investigates their potential as initiators for the ROP of rac-LA. Chain-end analysis and kinetic studies are included, providing the basis for mechanistic discussions. Chapter 4 focuses on the synthesis of stereoblock PLA materials in a stereospecific manner, and co-block PLA-PEG materials by the reinitiation of short-chain macroinitiators. The effect of stereocomplexation on the thermal properties of these materials is investigated. Chapter 5 concerns the synthesis of a series of isopropanol and zwitterionic rare earth complexes featuring the amine tris(phenolate) ligand motif. The potential of these complexes as initiators for the ROP of rac-LA is also investigated, but only slight stereocontrol was observed in selected cases. Chapter 6 provides details of procedures employed in the synthesis of ligands, complexes and polymers within this thesis, as well as details of the analytical techniques used in their characterisation.

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A Portuguese clay (BRN) from the North East city of Bragança was collected and characterized in terms of health treatment and applied towards the preparation of nanocomposites with Polylactide (PLA). The silt-clay fraction of BRN is mainly composed of smectite with less illite, kaolinite and other minerals. The physicochemical properties are applicable for the topical applications and are mainly influenced by smectite. With the hazardous elements present, further bioavailability tests should be conducted. PLA nanocomposites with BRN and Wyoming montmorillonite SWy-2 (MMT) were respectively prepared through the solution casting method with ultrasonic stirring and using cetyltrimethylammonium bromide (CTAB) as the surfactant. The X-ray diffraction patterns show the exfoliated structures in most samples. Thermal gravimetric analysis reveals the increased thermal stability of the nanocomposites. The complexes were also characterized by nitrogen adsorption, infrared analysis and nuclear magnetic resonance for comparing the differences between BRN and MMT.

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