Les nano-objets hybrides ou polymères connaissent un intérêt grandissant depuis plusieurs années mais peu sont étudiés sous irradiation. Dans ce travail, différents nano-objets ont été synthétisés et étudiés pour comprendre leur stabilité face à des rayonnements ionisants. Nous avons étudié l’effet de l’irradiation sur des copolymères à blocs amphiphiles pouvant s’organiser en micelles dans l’eau. Les objets varient par la nature de leur polymère hydrophobe et leur sensibilité aux rayonnements ionisants. Dans un cas, des polyméthacrylates ont été copolymérisés par ATRP à partir d’un PEG macro-amorceur. Dans un autre cas, pour accentuer l’effet de l’irradiation, un polysulfone aliphatique plus radiosensible, a été synthétisé via une polyaddition thiol-ène. Après nanoprécipitation, les objets ont été caractérisés avant et après irradiation par des techniques de diffusion et de chromatographie. En parallèle, on s’est intéressés également à des nanoparticules métalliques connues pour augmenter l’effet de l’irradiation. Des nanoparticules d’or greffées de polymères ont été synthétisées par voie « grafting to » après synthèse de macro-ligands par polymérisation radicalaire contrôlée. Après une caractérisation fine des objets, l’effet de l’irradiation a été étudié à la fois sur la taille des objets et la masse des polymères afin de déterminer la nature des phénomènes mis en jeu. / Hybrid and polymer nano-objects have known a growing interest these last years but few are studied under irradiation. In the present work, different nano-objects have been synthetized and studied to understand their stability towards ionizing rays. We have studied the effect of irradiation onto amphiphilic bloc copolymer that form micelles in water. Objects were varied by the nature of their hydrophobic bloc and their sensibility to ionizing rays. First, methacrylates were copolymerized by ATRP with a PEG macro-initiator. Secondly, to improve radiation effect, a more radiosensitive polymer, a polyolefinsulfone, was synthetized by a thiol-ene polyaddition. After nanoprecipitation, objects were caracterized before and after irradiation by scattering and chromatography techniques. In parallel we also studied metallic nanoparticles well known for improving irradiation effect. Polymer-grafted gold nanoparticles were synthetized via a “grafting to” technique, after the synthesis of macro-ligands by controlled radical polymerization. After a precise characterization of these objects, irradiation effect has been studied via changes in size and polymer mass. This will permit to determine the nature of induced phenomena.

The overall thrust of this dissertation is to gain a comprehensive understanding over the factors that govern the performance and behavior of ultra-thin, cross-linked polymer films. Poly(NIPAAm) was used as a model polymer to study volume phase transition in surface tethered networks. Poly(NIPAAm) undergoes a reversible phase transition at approximately 32°C between a swollen hydrophilic random coil to a collapsed hydrophobic globule state, thought to be caused by increased hydrophobic attractions between the isopropyl groups at elevated temperatures. We present a simple photochemical technique for fabricating structured polymer networks, enabling the construction of responsive surfaces with unique properties. The approach is based on the photo-cross-linking of copolymers synthesized from N-isopropylacrylamide and methacroyloxybenzophenone (MaBP). In order correlate layer swelling to the MaBP content, we have studied the swelling behavior of such layers in contact with aqueous solutions with neutron reflection. The cross-linked networks provide a three-dimensional scaffold to host a variety of functionalities. These networks serve as a platform which can be used to amplify small local perturbations induced by various stimuli like temperature, pH, solvent, ionic strength and peptide modified hydrogels to bring about a macroscopic change. Neutron reflection experiments have shown that the volume-phase transition of a surface-tethered, cross-linked poly(NIPAAm) network coincided with the two-phase region of uncross-linked poly(NIPAAm) in solution. Parallel measurements with ATR-FTIR investigating the effect of temperature, pH and salts suggest that the discontinuous transition is the result of cooperative dehydration of the isopropyl groups, with water remaining confined between amide groups in the collapsed state as weakly hydrogen bonded bridges. Hybrid polymers with specific peptide sequences have shown specific response to external cues such as pH and metal ions exhibiting unique phase behavior.

In the frame of this thesis different calix[4]resorcin- and calix[4]pyrogallolarene derivatives were used as platform for the synthesis of novel star polymers and dendritic structures. The objectives of this work can be portrayed under the following points: First: Synthesis and modification of calix[4]resorcin- and calix[4]pyrogallolarenes with a varying number and varying type of functional sites and their precise characterization by modern NMR techniques and single crystal X-ray diffraction. Second: Synthesis of well-defined star polymers and dendrimers with different number of arms and accordingly dendrons, based on calix[4]resorcin- and calix[4]pyrogallolarenes, via convenient polymerization and generation growth reactions and analysis of the obtained products by different methods (MALDI-TOF-MS, SEC-RI and SEC-MALLS, NMR).

Im Mittelpunkt dieser Arbeit stand die Darstellung sensitiver Blockcopolymere und deren Gele, die als Ausgangsmaterialien in Sensor- und Aktorsystemen einsetzbar sind. Die Vereinigung verschiedener Ansprechparameter stellt erhöhte Anforderung an die Synthese. Geringe Ansprechzeiten lassen sich mit einer Gelgröße im µm-Bereich erreichen. Hydrogele dieser Größenordnungen können durch nachträgliche Vernetzung funktioneller linearer Polymere ermöglicht werden. Die Makroinitiatormethode ermöglichte den Aufbau verschiedener linearer photovernetzbarer Blockcopolymere. Zum Einen wurde das temperatursensitive P(n-BuAc)-block-P(PNIPAAm-co-DMIAAm) erhalten, des Weiteren gelang die Darstellung der multi-sensitiven Blockcopolymere P2VP-block-P(NIPAAm-co-DMIAAm) und P4VP-block-P(NIPAAm-co-DMIAAm). Die Blockcopolymere wurden mit variierenden Blocklängen und Verhältnissen sowie mit unterschiedlichem Vernetzergehalt dargestellt. Die Charakterisierung der Blockcopolymere erfolgte mittels 1H-NMR-Spektroskopie, GPC-Messungen (Zusammensetzung) und DSC-Messungen (thermische Eigenschaften). Das Löslichkeitsverhalten in wässrigen Medien wurde durch Dynamische Lichtstreuung bestimmt. Die Beschreibung des Quellverhaltens der vernetzten Schichten erfolgte durch vornehmlich durch optische Methoden (SPR/OWS, WAMS, Ellipsometrie). Die Veränderung des E-Moduls in Abhängigkeit äußerer Parameter konnte mittels AFM untersucht werden. Die Reaktion der Schichten wurde gegenüber Temperatur, pH-Wert und Salzkonzentrationen getestet. Die charakterisierten Filme konnten im Anschluss als sensitive Schichten in piezoresistiven Sensorsystemen verwendetet werden.

Les travaux réalisés au cours de cette thèse concernent trois différentes techniques de formulation innovantes qui ont été étudiées en tant que procédés robustes et efficaces pour l’élaboration de polymères fonctionnels à architecture contrôlée ou bien de films minces réticulés. La première stratégie exploite le caractère orthogonal de la click chemistry la plus connue: la cycloaddition catalysée par le cuivre(I) entre un azoture et un alcyne (CuAAC). Nous avons développé deux stratégies monotopes tandem complémentaires alliant CuAAC et Polymérisation Radicalaire Contrôlée (PRC) afin d’obtenir efficacement des architectures complexes en une seule étape. La deuxième stratégie concerne l’utilisation de la chimie thiol-ène en tant que click chemistry pour la fonctionnalisation de polymères et la réalisation d’architectures bien définies. Une série de polymères portant des insaturations ont été synthétisés par des techniques de polymérisation contrôlée dans le but d’étudier et de comparer l’efficacité des couplages thiol-ène initiés thermiquement ou hotochimiquement. Dans cette étude, l’orthogonalité de la chimie thiol-ène avec la CuAAC a également été étudiée. La troisième stratégie est inspirée des récentes techniques d’élaboration de matériaux réticulés/fonctionnalisés par couplage des azotures avec des insaturations. Nous avons développé une nouvelle stratégie d’élaboration efficace de matériaux massifs et de films minces de PDMS réticulés par utilisation d’un diazoture comme agent réticulant. Cette étude est réalisée en combinant des expertises en rhéologie, chimie et en couches minces. / This thesis focuses on three different and innovative techniques studied as efficient and robust processes to elaborate functional polymers with controlled architecture or crosslinked materials and thin films. The first strategy exploits the orthogonal property of a famous click chemistry: the Copper (I)-catalyzed Azide–Alkyne Cycloaddition (CuAAC). We developed two complementary strategies based on the one-pot tandem combination of CuAAC and Controlled Radical Polymerisation techniques (CRP) to efficiently elaborate complex polymer architectures. The second strategy is focused on the thiol-ene chemistry as a click chemistry and its use for the functionalisation of polymers in order to obtain well defined architectures. A series of alkenefunctional polymers were synthesized by controlled polymerization techniques in order to investigate and compare the efficiency and orthogonality of both photochemically and thermally initiated thiol-ene click coupling reactions. Orthogonality of thiol-ene chemistry with CuAAC was also studied. The third strategy is inspired of new processes developed to perform crosslinked/functionalised materials by azide-ene couplings. We investigate a new strategy for the elaboration of crosslinked PDMS in bulk or in thin films with the use of a diazide as coupling agent. This last study combines analyses in rheology, chemistry and in thin layer.

Ce projet de thèse consistait à synthétiser de nouveaux bio-conjugués Lipide-Polymère fluorescents émettant dans le rouge lointain, composés d’une chaîne polymère portant à la fois de nombreux chromophores en position latérale et un lipide en extrémité de chaîne. La structure de ces bio-conjugués est basée sur des copolymères poly(N-acryloylmorpholine-co-N-acryloxysuccinimide), hydrophiles, réactifs, modulables et d’architecture contrôlée obtenus par le procédé RAFT. Les copolymères réactifs ont ensuite été utilisés pour le couplage, en position latérale, de chromophores émettant dans le rouge lointain. La stratégie utilisée pour la synthèse des bio-conjugués se divise en trois étapes : la synthèse d’Agents de Transfert de Chaîne (ATC) fonctionnalisés avec un lipide suivant un protocole déjà décrit suite à des travaux de notre équipe, et dont les étapes de purification ont été améliorées afin d’obtenir des ATC les plus purs possible (90% de pureté molaire) ; l’utilisation de ces ATC fonctionnels pour la synthèse de polymères α fonctionnels, et enfin, le couplage covalent, rapide et efficace, de chromophores en position latérale. Il a été mis en évidence que les ATC lipidiques permettent un très bon contrôle de la copolymérisation des monomères NAM et NAS. L’utilisation de la composition azéotropique pour ce couple de monomère permet également d’obtenir des chaînes polymère de microstructure très contrôlée et présentant des valeurs de Mn comprises entre 5 900 et 33 200 g.mol-1. Les propriétés optiques des bio-conjugués ont été déterminées, ce qui a permis de mettre en évidence que ces propriétés, et notamment le rendement quantique de fluorescence, sont très sensibles à la structure des bio-conjugués synthétisés. Tous les bio-conjugués présentent des brillances améliorées (jusqu’à 13 000 M-1.cm-1 dans l’eau et 50 0000 M-1.cm-1 dans CHCl3) par rapport à celle du chromophore. La capacité des bio-conjugués à interagir avec les bicouches lipidiques a été mise en évidence à travers l’utilisation de systèmes modèles (SUVs, LUVs et GUVs). Enfin, les évaluations biologiques réalisées ont montré à la fois une absence de cytotoxicité des bio-conjugués et une capacité de ces derniers à être internalisés rapidement (< 10 min) au sein de différentes lignées de cellules vivantes. / The aim of this study is to synthesize new far-red emitting fluorescent Lipid-Polymer conjugates, consisting of a polymer chain bearing both multiple fluorophores in lateral position and a lipid at one chain-end. These conjugates are based on an hydrophilic, reactive, flexible and controlled poly(N-acryloylmorpholine-co-N-acryloxysuccinimide) copolymer synthesized by the RAFT process. Multiple far-red emitting fluorophores were bound on the reactive copolymer in lateral position. The strategy used in this study consists of three different steps: Chain Transfer Agents (CTA) functionalized with a lipid were synthesized following a protocol already described in our team, the purity of these CTA was improved (90% molar purity); the use of these CTA for the synthesis of α functional polymers, and finally, the very efficient covalent binding of fluorophores in lateral position. We showed that the lipid-CTA enable a very good control of the NAM/NAS copolymerization. The azeotropic composition enables the synthesis of polymer chains with a controlled composition and with Mn values varying from 5 900 to 33 200 g.mol-1. The optical properties of the bio-conjugates were determined, and we showed that these properties (the fluorescence quantum yield especially) are structure sensitive. All of them show an improved brightness (13 000 M-1.cm-1 in water and 50 000 M-1.cm-1 in CHCl3) compared to the brightness of the free fluorophore. The ability of the bio-conjugates to interact with lipid bilayers was proved using model systems (SUVs, LUVs and GUVs). Finally, biological evaluations showed both an absence of cytotoxicity and an ability of the conjugates to be quickly internalized in leaving cells (< 10 min).

No description available.

Multifunctional monomers on the basis of acryl- and methacryl derivatives were synthesized and different protective groups were used. After polymerization the protective groups were removed by different methods. Various initiators for the NMP of the monomers were synthesized and the reaction conditions were optimized. The results showed that NMP was not a suitable method for multifunctional acryl- and methacryl derivatives to achieve well-defined homopolymers, although it was successful for control of polymerization of styrene and block copolymerization of multifunctional acryl- and methacryl derivatives with alkoxyamine terminated polystyrene. The ATRP of multifunctional acrylates and methacrylates has been successfully performed, as well as the block copolymerization of multifunctional acrylates and methacrylates. Relatively low polydispersities of the corresponding polymers (PD=1.18-1.36) and reasonably high rates of polymerization could be achieved when Me6TREN and PMDETA were used as ligands. However, the ATRP of multifunctional acrylamides and methacrylamides failed. The RAFT-polymerization of styrene, acrylamide and acrylate using BDTB as a CTA and AIBN as an initiator afforded polymers with narrow molecular weight distribution (PD=1.13-1.26). A kinetic investigation and the further synthesis of block copolymers using dithioester-terminated homopolymers as macroCTAs showed that the RAFT polymerization of acrylamide M9b proceeded in a living manner. However, BDTB does not control the reaction of methacrylic monomers, such as methacrylates and methacrylamides. The bulk phase behavior of the block copolymers were examined by means of DSC and the surface behaviors of block copolymers as thin layers were examined with AFM. Two-phase transitions in the block copolymers were observed clearly by DSC, indicative of the appearance of phase separations, which were seen in an AFM image. In conclusion, multifunctional acryl- and methacryl derivatives failed to achieve well-defined homopolymers by NMP. However, this method was successful for block copolymerization of multifunctional acryl- and methacryl derivatives with alkoxyamine terminated polystyrene. Multifunctional acrylates and methacrylates were successfully homopolymerized and block copolymerized by ATRP. Multifunctional acrylates and acrylamides were suitable for homopolymerization and block copolymerization by the RAFT process. Thus far, it is difficult to homopolymerize multifunctional methacrylamides in controlled way.

<p> A recently developed surface grafting technique, surface-initiated atom transfer radical polymerization (ATRP), has the ability to directly graft polymer chains with controllable chain lengths, densities and functionalities from various kinds of surfaces. This thesis has two main focuses. First is to study the use of this technique in grafting monomers with special structures and functionalities. The other is to apply this technique to the modification of reactive metal surfaces. </p> <p> Both of fluorinated polymers and polyhedral oligomeric silsesquioxane (POSS)-containing polymers have very interesting properties. In this thesis, for the first time, a highly fluorinated monomer, 2,2,2-trifluoroethyl methacrylate (TFEMA) and a POSS-containing monomer, POSS-MA were successfully polymerized from silicon wafers by surface-initiated ATRP. This is also the first work to use this technique to graft polymers with bulky, rigid side groups. </p> <p> To achieve very high grafting density is a big challenge for surface-initiated ATRP. We designed a novel surface-attachable difunctional initiator, 11-(2,2-bis(2bromo-2-methylpropionyloxy methyl)propionyloxy) undecyltrichlorosilane. With its help, the grafting density of PTFEMA was almost doubled, from 0.48 to 0.86chains/nm2. This is so far the most effective method to increase the grafting density. </p> <p> Unlike other kinds of materials, the surfaces of metals are active in electrochemical and acid/base reactions and this reactivity complicates A TRP reactions. With the help of triethoxysilane-based initiator and mild Fe(II)/Fe(III) catalyst system, various acrylic polymers were successfully grafted from flat nickel and copper surfaces by surface-initiated ATRP. This work provided a convenient method to prepare functional polymer coatings with very stable adhesions to the metal surfaces. The same strategy can be extended to the surface modification of a shape-memory-alloy, nitinol. </p> <p> Metal nanoparticles were also modified by this technique. Polymer shells were grafted from nickel nanoparticles surfaces. After the polymer grafting, both of the dispersibility and dispersion stability of nickel nanoparticles in appropriate solvents were greatly improved. </p> / Thesis / Doctor of Philosophy (PhD)

För att möjliggöra en hållbar utveckling skiftar många polymerforskares fokus just nu från att syntetisera polymerer från fossila resurser till att producera biobaserade polymerer från exempelvis träd. Av särskilt intresse är lignin, som utgör ungefär en tredjedel av allt växtmaterial men i nuläget oftast används som bränsle. Många forskare har undersökt de möjligheter som öppnas genom att bryta ner lignin och modifiera molekylerna som fås därigenom, såsom ferulsyra. Denna studie syftade till att modifiera ferulsyra till en styren-lik monomer med en karboxyl-substituent, och att testa vattenbaserad polymerisation av denna monomer.Det första steget i modifiering var dekarboxylering av ferulsyra. Detta utfördes genom upprepningar av tidigare studier där baskatalyserad dekarboxylering utfördes i polära aprotiska lösningsmedel. Efter flera försök hittades en fungerande metod, där trietylamin gav en dekarboxylering med högt utbyte efter tre timmar i dimetylformamid vid 100 °C. Att isolera produkten var också utmanande i början, men en trestegs-extraktion med H2O och Et2O som avslutades med en tvätt av saltvatten gav tillräcklig renhet. En ättiksyra-grupp adderades till fenolen med hjälp av en tvåstegsreaktion som hittades i litteraturen, men inte förrän ett dussin försök till nya metoder med kloroättiksyra gjorts utan framgång. I den fungerande metoden tillsattes en acetatgrupp med metylbromoacetat i återkokande aceton med kaliumkarbonat som bas, innan acetatet demetylerades av litiumhydroxid i en metanol/vattenblandning vid rumstemperatur.Den resulterande monomeren, 4-oxy-ättiksyra-3-methoxy-styren (OAMS), sampolymeriserades med styren, både i bulk- och emulsionspolymerisation. Bulksampolymeren hade en något högre molekylvikt och glastransitionstemperatur än homopolystyren, med en betydligt högre dispersitet. Emulsionspolymerisation var utmanande, eftersom OAMS inte är särskilt löslig i vare sig vatten eller styren, och i slutändan producerades inga tydliga resultat genom dessa försök.  Studiens huvudsakliga slutsats är att även om det är möjligt att syntetisera ren OAMS från ferulsyra, är användbarheten av denna molekyl som monomer i vattenbaserad polymerisering inte övertygande, eftersom den är så pass olöslig om inte bas tillsätts, vilket introducerar risken för hydrolys.Slutligen, även om studien ledde till få säkra slutsatser på grund av flera ofullständiga resultat, uppnåddes huvudsyftet att modifiera ferulsyra och testa polymerisation av den bildade monomeren. / To enable a sustainable development, scientific focus is shifting from synthesizing polymers from fossil-based resources to producing bio-based polymers from for example wood. Of particular interest is lignin, which makes up about a third of plant matter but is nowadays most commonly used as fuel. A great deal of research has explored the possibilities opened up by breaking down lignin and modifying its derived molecules, such as ferulic acid. This study aimed to modify ferulic acid into a styrenic monomer with an acidic substituent, and to investigate the aqueous polymerization of this monomer.The first step of modification was the decarboxylation of ferulic acid. This was attempted through recreations of previous studies where base-catalysed decarboxylation was carried out in aprotic polar solvents. After several trials, a successful procedure was found, where triethylamine gave a high-yield decarboxylation after three hours in dimethylformamide at 100 °C. Isolating the product was also initially challenging, but a three-step extraction with H2O and Et2O finished by a wash of brine gave sufficient purity.Adding an acetic acid-group to the phenol was achieved using a two-step procedure found in literature, but not before trying a dozen novel methods using chloroacetic acid without success. In the working procedure, an acetate group was added using methyl bromoacetate in refluxed acetone with potassium carbonate as base, before demethylating the acetate using lithium hydroxide in a methanol/water mix at room temperature. The resulting monomer, 4-oxy-acetic acid-3-methoxy-styrene (OAMS), was copolymerized with styrene, both in bulk and emulsion radical polymerization. The bulk copolymer displayed a slightly higher molecular weight and glass transition temperature than homopolystyrene, with a significantly higher dispersity. Emulsion polymerization was challenging, as OAMS is not very soluble in either water or styrene, and ultimately, no conclusive results were produced through this route.The study concluded that while it is possible to synthesize pure OAMS from ferulic acid, the degree of usability of this molecule as a monomer in aqueous polymerization is not certain, as it is hardly soluble without the addition of base, which introduces the risk of hydrolysis. Ultimately, although few solid conclusions could be drawn from this study due to several incomplete results, the core objective of modifying ferulic acid and testing polymerization of the resulting monomer was achieved.