Rozprawy doktorskie na temat „Atom Transfer Radical Polymerization Techniques”

Self-assembled monolayers and surface-initiated polymer, or polymer brushes, have attracted attention as they form dense layers with much higher structural order than bulk or solution polymers. Another field of research which has emerged over the last two decades is the field of organic and polymer electronics. In this field molecular order and surface modification are of major influence on the device performance, hence that both self-assembled monolayers as polymer brushes have been investigated to find applications in organic electronic devices. After an introduction into the field self-assembled monolayers, polymer brushes and organic electronics, the first part of this thesis focusses on three applications of surface modification techniques for applications in devices. Alignment of the active material is crucial for high mobilities in organic electronics. Chapter 2 discusses the synthesis of a liquid crystalline surface-initiated polymer and its application to induce strong homeotropic alignment. The alignment is homogeneous over large areas and can be patterned by combining the polymerization with soft lithographic techniques. Mobilities of organic electronic materials can also be strongly influenced by dopants in the material. In field-effect transistors the positioning of the dopant is thought to be crucial, as the conductance predominantly takes place in only a small channel near the dielectric interface. In chapter 3 dopant functionalized monolayers and polymer brushes are presented which enable the localized deposition of dopants in the channel of organic transistors. It is shown that the mobility of charges and hence the device performance is affected by the introduction of this dopant layer. Polymer brushes have been suggested for the fabrication of highly ordered semiconducting polymers. In chapter 4 the use of a thiophene functionalized polymer brush is shown, that can be used as a template for the subsequent growth of highly conjugated surface grafted polythiophene layers. Thick polythiophene layers are obtained, that are low in roughness and show photoluminescence and polychromism upon doping. The second part (chapter 5 and 6) of this thesis presents new techniques for surface polymerizations. It is attractive to investigate reduction of reactor volume for polymer brush growth. Chapter 5 discusses a method to achieve volume reduction by back-filling the superfluous volume with beads. It is found that this influences the polymerization kinetics significantly. The combined advantages of less volume and enhanced reaction speeds enable reduction of the total amount of monomer needed by up to 90%. Chapter 6 presents a controlled way to convert initiators for atom transfer radical polymerization into initiators for nitroxide mediated polymerization. In this way mixed polymer brushes and block co-polymer brushes become accessible. This combination makes it an attractive tool to fabricate complex polymer architectures. The technologies used in this thesis show that the synthesis of polymer brushes enable the fabrication of complex architectures without the wastes normally associated with surface-initiated polymers. Combined with several functionalized polymer brushes with properties that enhance order, influence mobility or serve as template for the growth of surface attached conjugated polymers this shows the high potential for the application of surface-initiated polymers in organic electronics.

Ce travail concerne la modification de surface de nanoparticules magnétiques (MNP) par des copolymères réactifs renfermant des cycles azlactone, aux fins de l’élaboration de nano-supports destinés à l’immobilisation de biomolécules. Trois stratégies basées sur des techniques de polymérisation radicalaire contrôlée ont été mises en œuvre.Dans la première, un copolymère poly(méthacrylate de poly(éthylène glycol)-stat-2-vinyl-4,4-diméthylazlactone) (poly(PEGMA-stat-VDM)) a été préparé par polymérisation radicalaire par transfert d’atome (ATRP) selon la technique « grafting from » à partir des MNP et utilisé pour la bioconjugaison de thymine peptide nucleic acid (PNA). La présence de l’écorce polymère et l’immobilisation du PNA ont été confirmées par différentes techniques complémentaires (FTIR, VSM).La deuxième stratégie est basée sur l’élaboration de MNP greffées pour la bioconjugaison de l’acide folique, via l’ARTP du PEGMA et de la VDM. L’analyse par microscopie électronique à transmission (TEM) a montré qu’après bioconjugaison les MNP possèdent une très bonne aptitude à la dispersion en milieu aqueux.La troisième stratégie met en œuvre la technique «grafting onto » de copolymères poly(oxyde d’éthylène)-bloc-poly(2-vinyl-4,4-dimethylazlactone) (PEO-b-PVDM) pour la préparation de nanosupports magnétiques recyclables. Des copolymères à blocs PEO-b-PVDM ont été préparés par la technique de polymérisation RAFT puis greffés sur des MNP fonctionnalisées amino-silane. Les analyses en TEM et par spectroscopie de corrélation de photons ont révélé l’aptitude à la dispersion aqueuse et à la formation de nanoclusters. Les clusters ainsi obtenus ont été utilisés en tant que nanosupports magnétiques recyclables pour l’adsorption d’anticorps<br>We herein report the surface modification of magnetite nanoparticle (MNP) with copolymers containing active azlactone rings via a grafting ‘from’ and grafting ‘onto’ controlled radical polymerization (CRP) for use as a nano-solid support for immobilization with biomolecules. Three different approaches were presented as following. First, synthesis of poly(poly(ethylene glycol) methyl ether methacrylate-stat-2-vinyl-4,4-dimethylazlactone) (PEGMA-stat-VDM)-grafted MNP via a grafting ‘from’ atom transfer radical polymerization (ATRP) and its application as a platform for conjugating thymine peptide nucleic acid (PNA) monomer were presented. The presence of polymeric shell and the immobilization of thymine PNA on MNP core were confirmed by fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometry (VSM) techniques. The second strategy is based on the synthesis of MNP grafted with PEGMA and VDM via ATRP for conjugation with folic acid (FA). The existence of PEGMA and VDM in the structure was characterized by FTIR, TGA and VSM. After the FA conjugation, Transmission Electron Microscopy (TEM) results indicated that the FA-conjugated MNP having high VDM content exhibited good dispersibility in water.Third, the synthesis of MNP grafted with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) (PEO-b-PVDM) block copolymer via a grafting ‘onto’ strategy and its application as recyclable magnetic nano-support for adsorption with antibody were studied. PEO-b-PVDM diblock copolymers were first synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization and then grafted onto amino-functionalized MNP. TEM images and photo correlation spectroscopy (PCS) indicated an improvement in the particle dispersibility in water after coating with the copolymers. The nanoclusters with PEO-b-PVDM copolymer coating were used as recyclable magnetic nano-supports for adsorption with antibody

<p>Atom transfer radical polymerization (ATRP) has proven to be a powerful technique to obtain polymers with narrow polydispersities and controlled molecular weight. It also offers control over chain-ends. The technique is the most studied and utilized of thecontrolled/”living” radical polymerization techniques since a large number of monomerscan be polymerized under simple conditions. ATRP can be used to obtain polymer graftsfrom multifunctional substrates. The substrates can be either soluble (i. e. based ondendritic molecules) or insoluble (such as gold or silicon surfaces). The large number ofgrowing chains from the multifunctional substrates increases the probability of inter-and intramolecular reactions. In order to control these kinds of polymerizing systems, andsuppress side-reactions such as termination, the concentration of propagating radicalsmust be kept low. To elaborate such a system a soluble multifunctional substrate, based on 3-ethyl-3-(hydroxymethyl)oxetane, was synthesized. It was used as a macroinitiatorfor the atom transfer radical polymerisation of methyl acrylate (MA) mediated byCu(I)Br and tris(2-(dimethylamino)ethyl)amine (Me6-TREN) in ethyl acetate at room temperature. This yielded a co-polymer with a dendritic-linear architecture. Since mostsolid substrates are sensitive to the temperatures at which most ATRP polymerisations are performed, lowering the polymerization temperatures are preferred. ATRP at ambienttemperature is always more desirable since it also suppresses the formation of thermally formed polymer. The macroinitiator contained approximately 25 initiating sites, which well mimicked the conditions on a solid substrate. The polymers had low polydispersity and conversions as high as 65% were reached without loss of control. The solid substrateof choice was cellulose fibers that prior to this study not had been grafted through ATRP.As cellulose fibers a filter paper, Whatman 1, was used due to its high cellulose content.The hydroxyl groups on the surface was first reacted with 2-bromoisobutyryl bromidefollowed by grafting of MA. Essentially the same reaction conditions were used that hadbeen elaborated from the soluble substrate. The grafting yielded fibers that were very hydrophobic (contact angles>100°). By altering the sacrificial initiator-to-monomer ratiothe amount of polymer that was attached to the surface could be tailor. PMA with degreesof polymerization (DP’s) of 100, 200 and 300 were aimed. In order to control that thepolymerizations from the surface was indeed “living” a second layer of a hydrophilicmonomer, 2-hydroxymethyl methacrylate (HEMA), was grafted onto the surface. Thisdramatically changed the hydrophobic behavior of the fibers.</p><br>QC 20100524

Surface tethered bottle-brush co-polymers are prepared by ATRP grafting of the macroinitiator brush backbone onto plasmachemical deposited poly(vinylbenzyl chloride) initiator nanofilms, followed by ATRP growth of the side chains (bristles). Lateral force scanning probe microscopy demonstrates that poly(glycidyl methacrylate)-graft-poly(sodium 4-styrenesulfonate) bottle-brush decorated surfaces give rise to an enhancement in lubrication. Patterned polymer brushes are fabricated using molecular scratchcard lithography, where a functional top nanolayer (acting as a resist) is selectively removed using a scanning probe tip to expose underlying ATRP initiator sites. The lateral spreading of grafted polymer brush patterns across the adjacent functional resist surface is reversibly actuated by solvent exposure. Macroporous poly(vinylbenzyl chloride) scaffolds are used for ATRP initiation to generate polymer brushes and thereby actuate pore size. These functionalised macroporous scaffolds are fabricated by a decoupled two-step approach comprising plasmachemical deposition of the host material followed by spontaneous emulsion formation using amphiphilic species. Finally, charge nanopatterning onto polymer film surfaces is accomplished by using an SPM probe tip to create localised corona discharge electrification. The efficacy of surface charging is shown to correlate strongly to the polymer substrate hydrophilicity. Localised plasma generation using a scanning probe microscope tip is then demonstrated to actuate the movement of ATRP surface grafted polyelectrolyte and polyzwitterionic brushes. The raising or retraction of polymer brushes can be controlled by varying the SPM tip polarity.

Controlled radical polymerizations (CRPs) are among the most powerful methods to obtain polymers with well-defined properties and high commercial value. Atom transfer radical polymerization (ATRP) is probably the most widely used CRP, in academia and industry, thanks to its versatility and simplicity. In ATRP, a metal complex in a low oxidation state, MtzLm (typically a copper-amine system, [CuIL]+) reacts with a dormant polymeric chain Pn–X (where X = Cl, Br) to produce radicals Pn• that can propagate, in the bulk of the solution, by addition to monomer units. In this reaction, the copper complex is oxidized and binds to X–, generating the deactivating species [X-CuIIL]+, which traps the propagating species. ATRP equilibrium is shifted towards the dormant species Pn-X, so that Pn• concentration is very low, and the probability of radical-radical termination events is minimized. Growth of all chains begins virtually at the same time, thanks to the use of alkyl halide (RX) initiators that are more reactive than the dormant species, Pn-X. In such conditions, chain growth is homogenous, and it is possible to obtain polymers with predetermined molecular weight, narrow molecular-weight distribution and high chain-end fidelity. ATRP allows to tailor macromolecules with specific compositions, architectures and position of functional groups. The aim of this thesis is to contribute to both the understanding and development of ATRP catalyzed by copper complexes, using electrochemical methods as equally analytical tools and efficient means of triggering and controlling the polymerization. The work focused on spreading the use of such systems to efficiently control the polymerization of a series of important monomers. Moreover, the investigated ATRP systems can be considered also “green” for several reasons: (i) most of the work regards the study and development of the reaction in green solvents in which copper complexes generally have high catalytic activity; (ii) electrochemical methods for catalyst regeneration (electrochemically mediated ATRP, eATRP) allowed triggering the polymerization with low loadings of copper complexes; (iii) ionic liquids, a class of non-flammable and easily recyclable solvents, were explored as potential media for eATRP; (iv) the mechanism of catalytic halogen exchange was investigated and defined, abridging the synthesis of block copolymers. ATRP catalysts were investigated in the ionic liquid 1-butyl-3-methylimidazolium triflate ([BMIm][OTf]). Both Cu/L speciation and reactivity were found to be suitable for a well-controlled polymerization process. Polymerizations were conducted with electrochemical (re)generation of the active [CuIL]+ complex (eATRP). eATRP of methyl acrylate was investigated in detail by varying a series of parameters such as applied potential, temperature, degree of polymerization and catalyst load ([CuIITPMA]2+, TPMA = tris(2-pyridylmethyl)amine). Application of an electrochemical switch and chain extension with acrylonitrile via catalytic halogen exchange (cHE) proved the livingness of the polymerizations. Experiments triggered in recycled ionic liquid proved that eATRP tolerates well the recycled solvent; polymerizations exhibited good control and high conversion. Block copolymers (BCP) have relevance in a vast range of applications in everyday life. BCP of acrylonitrile (AN) and butyl acrylate (BA) were investigated as precursors for mesoporous carbons. Thus, eATRP of acrylonitrile was studied considering several aspects, including the effect of applied potential, degree of polymerization, C-X nature and initiator structure. A macroinitiator of PAN was then extended with BA to form PAN-b-PBA copolymer as a precursor for mesoporous carbons. BCP can be obtained also by extension of a PBA chain with AN via cHE, thus avoiding purification procedures and reactivity mismatch when crossing from a less reactive monomer to a more reactive one. cHE was proved to be an efficient tool of polymerization by both SARA and eATRP, in a range of solvents, including water. Methyl methacrylate (MMA) was polymerized thanks to cHE in [BMIm][OTf] and ethanol, to solve the issue of penultimate effect. Fine tuning of the electrolysis conditions afforded PMMA with low dispersion. Further improvements were obtained by using [CuIIPMDETA]2+ as an inexpensive and efficient catalyst in alternative to [CuIITPMA]2+. Tacticity analysis of PMMA obtained in [BMIm][OTf] and ethanol confirmed the poor ability of the ionic solvent to induce stereocontrol to the polymerization. Pyridinic complexes such as [CuIITPMA]2+ are stable in very acid conditions (pH = 1). This allowed unprecedented control over conditions of macromolecular growth in water. In addition, it opened a new avenue for the polymerization of ionic liquid monomers (ILMs), a class of building blocks that can give a plethora of new materials. The main reason preventing ATRP of ILM is a cyclization reaction involving the chain-end with the terminal halogen as a leaving group, as in the case of methacrylic acid. Application of three strategies previously developed for ATRP of methacrylic acid allowed to dramatically improve conversion and control over ILMs polymerization. (i) Using C-Cl chain end functionality, which is much more stable than C-Br, (ii) lowering further the pH to completely convert free carboxylate ions to carboxylic acid, which is a much weaker nucleophile, and (iii) enhancing the polymerization rate to avoid the negative contribution of the cyclization side reaction, allowed synthesis of well-controlled high molecular weight poly(ionic liquids), PILs, with degree of polymerization > 500. A simple (poly)halogenated organic initiator such as 2,2-dichloropropionic acid was used to produce linear homotelechelic PILs. Electrochemically mediated ATRP allowed exceptional control over CuI (re)generation. For this reason, it was decided to study the eATRP of vinyl chloride, which was considered impossible until now. The polymerization, triggered in a pressure-resistant electrochemical reactor, was controlled, fast and afforded an acceptable conversion. In addition to linear PVC, a star PVC was also synthesized, highlighting the flexibility of eATRP. In the star architecture, the electrochemical polymerization was by far superior to the chemical one (SARA ATRP). The success of this polymerization has categorically denied the SET-LRP mechanism and its assumptions. One of the crucial properties of electrochemical eATRP is the inert role played by the cathode material used for the regeneration of [CuIL]+. Any electrode material with good stability in the reaction medium can be used as a cathode. It was therefore decided to study the polymerization of an acrylate using the surface of a stainless steel (SS304) reactor exposed to the polymerization mixture as a cathode. In this way, the reactor has the dual function of electrode and place where the reaction takes place. The results showed that polymerization is fast, controlled and reaches high conversions. Moreover, the absence of release of metal ions during the reaction (Fe, Ni, Cr) confirmed that the polymerization takes place via electrochemical reduction of CuII to CuI, while SS304 acts only as an electron reservoir, not chemically involved in ATRP activation. Such simple and cheap electrochemical setup can make the scale-up of the eATRP a reality in the short term and open new economic prospects.<br>Le polimerizzazioni radicaliche controllate (CRP) sono riconosciute come i metodi più potenti per ottenere polimeri con struttura macromolecolare ben definita e alto valore commerciale. La polimerizzazione radicalica a trasferimento atomico (ATRP) è probabilmente la CRP più utilizzata, in accademia e industria, grazie alla sua versatilità e semplicità. Nell’ATRP, un complesso metallico a basso stato di ossidazione, MtzLm (tipicamente un sistema rame-ammina, [CuIL]+) reagisce con una catena polimerica dormiente Pn-X (dove X = Cl, Br) per produrre radicali Pn•. Questi propagando nel bulk della soluzione, crescono aggiungendo unità monomeriche. In questo processo, il complesso di rame viene ossidato e si lega a X-, generando la specie disattivante [X-CuIIL]+, che intrappola la specie propagante. L'equilibrio di ATRP è fortemente spostato verso la specie dormiente Pn-X, cosicché la concentrazione di radicali sia molto bassa e la probabilità di eventi di terminazione bimolecolare sia ridotta al minimo. La crescita inizia praticamente allo stesso tempo per tutte le catene grazie a iniziatori (alogenuro alchilico) molto efficienti (RX). In tali condizioni, la crescita delle catene è omogenea ed è possibile ottenere polimeri con peso molecolare predeterminato, distribuzione stretta dei pesi molecolari e alta ritenzione della funzionalità di fine catena. L’ATRP consente di costruire dunque macromolecole con specifiche composizioni, architetture e posizionamento dei gruppi funzionali. Lo scopo di questa tesi è di contribuire alla comprensione e allo sviluppo dell’ATRP catalizzata da complessi di rame, utilizzando metodi elettrochimici sia come strumenti analitici che come strumenti per eseguire e controllare la polimerizzazione. Il lavoro si è concentrato sulla diffusione dell'uso di tali sistemi per controllare in modo efficiente la polimerizzazione di una serie di monomeri rilevanti. I sistemi investigati per ATRP possono essere considerati anche "green" per diversi motivi: (i) la maggior parte del lavoro riguarda lo studio e lo sviluppo della reazione in solventi green, generalmente caratterizzati da un'elevata attività catalitica; (ii) i metodi elettrochimici per la rigenerazione del catalizzatore (ATRP mediata elettrochimicamente, eATRP) permette la polimerizzazione con limitata quantità di complessi di rame; (iii) i liquidi ionici, una nuova classe di solventi non infiammabili e facilmente riciclabili, sono stati esplorati come potenziali solventi per eATRP; (iv) il meccanismo di halogen exchange catalitico (cHE) è stato studiato e sviluppato, facilitando la sintesi di copolimeri a blocchi. I catalizzatori ATRP sono stati studiati nel liquido ionico 1-butil-3-metilimidazolio triflato. Sia la speciazione che la reattività di Cu/L sono risultate in linea per un processo di polimerizzazione ben controllato. Le polimerizzazioni sono state condotte con la (ri)generazione elettrochimica del complesso attivo [CuIL]+ (eATRP). L'eATRP del metil acrilato è stata studiata in dettaglio variando una serie di parametri come: potenziale applicato, temperatura, grado di polimerizzazione e carico di catalizzatore di Cu/TPMA (TPMA = tris(2-piridilmetil)ammina). Un interruttore elettrochimico e l'estensione della catena con acrilonitrile (grazie al meccanismo di halogen exchange catalitico) hanno dimostrato la presenza della funzionalità di fine catena. Le polimerizzazioni ottenute tramite liquido ionico riciclato hanno dimostrato che eATRP tollera bene anche un solvente riciclato. I copolimeri a blocchi (BCP) hanno rilevanza in una vasta gamma di applicazioni nella vita di tutti i giorni. BCP di acrilonitrile (AN) e butil acrilato (BA) sono stati studiati come precursori di carbonio mesoporoso. Pertanto, eATRP di acrilonitrile è stata introdotta e studiata nei diversi aspetti, come: effetto del potenziale applicato, del grado di polimerizzazione, della natura di C-X e della struttura dell'iniziatore. Un macroiniziatore di PAN è stato quindi esteso con BA per formare il copolimero PAN-b-PBA come precursore del carbonio mesoporoso. I BCP possono essere ottenuti anche via cHE, evitando così le procedure di purificazione e la differenza di reattività quando si passa da un monomero meno reattivo a uno più reattivo. Il cHE si è dimostrato strumento efficace di polimerizzazione sia da SARA che da eATRP, in una gamma di solventi incluso DMSO e acqua. Il metil metacrilato (MMA) è stato polimerizzato grazie al cHE in liquido ionico ed etanolo, per risolvere il problema dell’effetto del penultimo. La messa a punto delle condizioni di elettrolisi ha permesso di ottenere PMMA a bassa dispersione. Ulteriori miglioramenti sono stati ottenuti utilizzando [CuIIPMDETA]2+ come catalizzatore come alternativa economica ed efficiente a Cu/TPMA. L'analisi della tatticità del PMMA ottenuta in [BMIm][OTf] e l'etanolo ha confermato la scarsa capacità del solvente ionico di indurre stereocontrollo durante la polimerizzazione. I complessi piridinici, come Cu/TPMA, stabili fino a condizioni molto acide (pH ⁓1) hanno permesso di ottenere poli(liquidi ionici). Hanno aperto infatti una nuova strada per la polimerizzazione di monomeri liquidi ionici, una classe di molecole che può dare una pletora di nuovi materiali polimerizzati mediante ATRP. La ragione principale che impedisce l'ATRP di ILM è una reazione di ciclizzazione che coinvolge l'estremità della catena, con l'alogeno terminale come gruppo uscente, come nel caso dell'acido metacrilico. Le stesse tre strategie usate per l’acido metacrilico hanno permesso di migliorare drasticamente la conversione e il controllo sulla polimerizzazione di ILM: (i) usando la funzionalità di fine catena C-Cl, che è molto più stabile di C-Br; (ii) abbassando il pH per convertire completamente gli ioni carbossilato liberi in acido carbossilico, che è un nucleofilo molto più debole; (iii) migliorare la velocità di polimerizzazione per evitare il contributo negativo della reazione di ciclizzazione. Tali condizioni hanno permesso la sintesi di poli(liquidi ionici) (PIL) ben controllati ad alto peso molecolare fino a grado di polimerizzazione 1000. Un semplice iniziatore organico (poli)alogenato come acido 2,2-dicloropropionico è stato utilizzato per produrre un PIL lineare telechelico. L’insieme di questi risultati può consentire una più facile implementazione e scalabilità industriale dell’eATRP. Per questo motivo, è stato deciso di studiare l’eATRP del cloruro di vinile, considerata finora impossibile. La polimerizzazione, effettuata in un reattore elettrochimico resistente alla pressione, è controllata, veloce e con una conversione buona in tempi ragionevoli. Oltre al classico PVC lineare, è stato anche sintetizzato un PVC a stella, evidenziando la flessibilità dell'eATRP. Nell'architettura a stella, la polimerizzazione elettrochimica si è dimostrata di gran lunga superiore a quella chimica (SARA ATRP). Il successo di questa polimerizzazione ha smentito il meccanismo SET-LRP e le sue assunzioni. Una delle proprietà dell’eATRP è la tolleranza al materiale catodico utilizzato per la rigenerazione di [CuIL]+. Si è deciso dunque di studiare la polimerizzazione di un acrilato usando la superficie del reattore esposto alla miscela di polimerizzazione come elettrodo. In questo modo il reattore ha la duplice funzione di elettrodo e luogo fisico in cui avviene la reazione. I risultati hanno mostrato che la polimerizzazione è veloce e controllata, raggiungendo conversioni elevate in breve tempo. Inoltre, l'assenza di rilascio di ioni metallici durante la reazione (Fe, Ni, Cr) da parte dell’acciaio conferma che la polimerizzazione avviene elettrochimicamente, l'acciaio agisce solo come un serbatoio di elettroni e non è chimicamente coinvolto. Una tale impostazione elettrochimica, semplice ed economica, può rendere l'eATRP una tecnica commerciale a breve termine e aprire nuove prospettive economiche.

In this work, methylmethacrylate, MMA was polymerized by ATRP method to obtain low molecular weight living polymers. The initiator was p-toluenesulfonylchloride and catalyst ligand complex system were CuCl-4,4&rsquo<br>dimethyl 2,2&rsquo<br>bipyridine. Polymers with controlled molecular weight were obtained. The polymer chains were shown by NMR investigation to be mostly syndiotactic. The molecular weight and molecular weight distribution of some polymer samples were measured by GPC method. The K and a constants in [h]=K Ma equation were measured as 9.13x10-5 and 0.74, respectively. FT-IR and X-Ray results showed regularity in polymer chains. The molecular weight-Tg relations were verified from results of molecular weight-DSC results.

<p>Controlled radical polymerization has proven to be a viableroute to obtain polymers with narrow polydispersities (PDI's)and controlled molecular weights under simple reactionconditions. It also offers control over the chain-]ends of thesynthesized polymer. Atom transfer radical polymerization(ATRP) is the most studied and utilized of these techniques. Inthis study ATRP has been utilized as a tool to obtain differentcomplex macromolecular structures.</p><p>In order to elaborate a system for which a multitude ofchains can polymerize in a controlled manner and in closeproximity to one another, a multifunctional initiator based onpoly(3-ethyl-3-(hydroxymethyl)oxetane was synthesized. Themacroinitiator was used to initiate ATRP of methyl acrylate(MA). The resulting dendritic-]linear copolymer hybrids hadcontrolled molecular weights and low PDI's. Essentially thesame system was used for the grafting of MA from a solidsubstrate, cellulose. A filter paper was used as cellulosesubstrate and the hydroxyl groups on the cellulose weremodified into bromo-]ester groups, known to initiate ATRP.Subsequent grafting of MA by ATRP on the cellulose made thesurface hydrophobic. The amount of polymer that was attached tothe cellulose could be tailored. In order to control that thesurface polymerization was -eliving-f and hence that thechain-]end functionality was intact, a second layer of ahydrophilic monomer, 2-hydroxyethyl methacrylate, was graftedonto the PMA- grafted cellulose. This dramatically changed thehydrophilicity of the cellulose.</p><p>Dendronized polymers of generation one, two and three weresynthesized by ATRP of acrylic macromonomers based on2,2-bis(hydroxymethyl)propionic acid. In the macromonomerroute, macromonomers of each generation were polymerized byATRP. The polymerizations resulted in polymers with low PDI's.The kinetics of the reactions were investigated, and thepolymerizations followed first-order kinetics when ethyl2-bromopropionate was used as the initiator. In the-egraft-]onto-f route dendrons were divergently attached to adendronized polymer of generation one, that had been obtainedby ATRP.</p>

This work explores the application and control of heterogeneity within ATRP. The term “heterogeneity” can be applied to polymers in many ways however, this dissertation focuses on molecular weight distribution (MWD) and copolymer composition. The first chapter reviews not only controlled radical polymerizations (CRPs) but also current research on heterogeneity within CRPS, including methods to reduce or purposefully incorporate MWD into polymers as well as advances made to intricate copolymer compositions such as sequence controlled or gradient copolymers. Chapters II and III discuss avenues to reduce MWD values in homogeneous and heterogeneous media, respectively. Dual initiating systems are utilized to provide well controlled polymerizations of methyl acrylate in Chapter II while Chapter III details the synthesis of new active yet hydrophobic ligands for use in ARGET ATRP miniemulsion polymerizations. On the other hand, work in Chapter IV focuses on synthesizing block copolymers with broad MWD through the manipulation of catalyst concentration in ARGET ATRP. Chapter V utilizes the concepts and procedures of Chapter IV to generate gradient copolymers with broad MWD whose quality of gradient architecture is with MWD values. ABA triblock copolymers with disperse center blocks were generated in Chapter VI, however this was not accomplished with ATRP but with polycondensation. From the disperse telechelic macroinitiator synthesized via polycondensation, outer blocks were polymerized under ATRP conditions. The final chapter studies the effects of composition (random, block, and gradient) and topology (linear and star) copolymers utilized as polymeric surfactants in emulsions.

Thesis (MSc)--Stellenbosch University, 2003.<br>ENGLISH ABSTRACT: Controlled free radical polymerisation techniques offer several practical and theoretical advantages compared to many other polymerisation techniques. Living polymerisation techniques such as anionic polymerisations require the total exclusion of impurities such as oxygen and moisture. Controlled free radical polymerisations, however, do not require such stringent methods of practice. This is very advantageous for industrial purposes. Atom Transfer Radical Polymerisation (ATRP) is a form of a controlled/living free radical polymerisation technique by which one is able to synthesize controlled architectural structures and predetermine the molecular weights of macromolecules. The monomers that were investigated for this research project include methyl methacrylate (MMA), 4-vinylpyridine (4VP) and lauryl methacrylate (LMA). The latter two monomers (4VP and LMA) are not commonly used in ATRP-mediated reactions. The synthesis of block copolymers ofMMA and LMA were attempted. The homopolymerisation of 4VP did not give the control expected when polymerising by means of ATRP. This prompted an investigation into possible side reactions that could take place with 4VP in this specific ATRP system. This included possible quatemization of 4VP with the alkyl halide initiator species.<br>AFRIKAANSE OPSOMMING: Beheerde vrye-radikaalpolimerisasietegnieke bied verskeie praktiese en teoretiese voordele bo verskeie ander vrye-radikaalpolimerisasietegnieke. Lewende polimerisasietegnieke soos anioniese polimerisasie, vereis die totale uitsluiting van onsuiwerhede soos suurstof en water. Beheerde vrye-radikaalpolimerisasies vereis egter nie sulke streng reaksiekondisies nie. Hierdie is baie voordelig vir industriële doeleindes. Atoomoordragradikaalpolimerisasie (ATRP) is 'n tipe beheerde/lewende vryeradikaalpolimerisasietegniek wat dit moontlik maak om die samestelling en struktuur van makromolekules asook die molekulêre massa presies te beheer. In hierdie studie is die monomere metielmetakrilaat (MMA), 4-vinielpiridien (4VP) en laurielmetakrilaat (LMA) bestudeer. Laasgenoemde twee monomere (4VP en LMA) word beskou as ongewone monomere om in ATRP-sisteme te gebruik. Daar is gepoog om blok kopolimere van MMA en LMA te sintetiseer. Die homopolimerisasie van 4VP het minder beheer gelewer as wat by beheerde vrye-radikaal sisteme soos hierdie verwag word. Na aanleiding van hierdie resultate is 'n ondersoek geloods om die moontlike newereaksies van 4VP in hierdie spesifieke ATRP-sisteem te ondersoek. Daar is gepoog om te bewys dat die alkielchloriedinisieerder verdwyn deur kwatemisasie met 4VP.

The potential use of renewable, bio-based polymers in high-technological applications has attracted great interest due to increased environmental concern. Cellulose is the most abundant biopolymer resource in the world, and it has great potential to be modified to suit new application areas. The development of controlled polymerization techniques, such as atom transfer radical polymerization (ATRP), has made it possible to graft well-defined polymers from cellulose surfaces. In this study, graft-modification of cellulose substrates by ATRP was explored as a tool for tailoring surface properties and for the fabrication of functional cellulose surfaces. Various native and regenerated cellulose substrates were successfully graft-modified to investigate the effect of surface morphology on the grafting reactions. It was found that significantly denser polymer brushes were grafted from the native than from the regenerated cellulose substrates, most likely due to differences in surface area. A method for detaching the grafted polymer from the substrate was developed, based on the selective cleavage of silyl ether bonds with tetrabutylammonium fluoride. The results from the performed kinetic study suggest that the surface-initiated polymerization of methyl methacrylate from cellulose proceeds faster than the concurrent solution polymerization at low monomer conversions, but slows down to match the kinetics of the solution polymerization at higher conversions. Superhydrophobic and self-cleaning bio-fiber surfaces were obtained by grafting of glycidyl methacrylate using a branched graft-on-graft architecture, followed by post-functionalization to obtain fluorinated polymer brushes. AFM analysis showed that the surface had a micro-nano-binary structure. It was also found that superhydrophobic surfaces could be achieved by post-functionalization with an alkyl chain, with no use of fluorine. Thermo-responsive cellulose surfaces have been prepared by graft-modification with the stimuli responsive polymer poly(N-isopropylacrylamide) (PNIPAAm). Brushes of poly(4-vinylpyridine) (P4VP) rendered a pH-responsive cellulose surface. Dual-responsive cellulose surfaces were achieved by grafting block-copolymers of PNIPAAm and P4VP.<br>QC 20100804

Philosophiae Doctor - PhD<br>A variety of nitrogen based dendritic ligands have been synthesized and used in copper mediated Atom Transfer Radical Polymerization (ATRP) of MMA. These ligands were derived from the commercially available Generation 1 polypropyleneimine dendrimer DAB-(NH2)4. The first set of ligands was synthesized by reacting DAB-(NH2)4 with aromatic aldehydes such as 2-pyridinecarboxyaldhyde and 4-t-butyl benzaldehyde to form imine functionalized dendrimers. Analogous secondary amine functionalized dendrimers were also synthesized by reducing the abovementioned imine functionalized dendrimers using sodium borohydride. The ligands produced were characterized by 13C / 1H NMR, and infra-red spectroscopy as well as elemental analysis to confirm its structure. The ligands were then used in copper mediated ATRP of MMA. The resulting polymer solutions were analyzed by Gas Chromatography (GC) to monitor the monomer conversion while the isolated polymers were analyzed by gel permeation chromatography (GPC) for molecular weight determination. Results showed that the primary and secondary amine and imine dendritic ligands were not efficient in promoting ATRP reactions. This led to the modification of DAB-(NH2)4 using methyl methacrylate to replace the peripheral amino groups of the DAB-(NH2)4 with tertiary amine groups. A second generation tertiary amine dendrimer was also synthesized in a similar fashion. The ligands obtained were then characterized using 13C and 1H NMR spectroscopy. The tertiary amine dendrimers were used in copper mediated ATRP of MMA. The polymerization medium was analyzed over time using GC to monitor monomer conversion while GPC was used for molecular weight determination of the resulting polymers. The results obtained using the methyl methacrylate modified ligands indicated that in the case of MMA polymerization, these ligands essentially conformed to the requirements of a good ATRP system. However in the preliminary studies, when employed in copper mediated ATRP of styrene, these ligands did not perform well. Further investigation is needed to improve the performance of these ligands in styrene polymerization under ATRP conditions.<br>South Africa

Atom transfer radical polymerization (ATRP) is one of the most commonly employed techniques for controlled radical polymerization. ATRP has great potential for the development of new materials due to the ability to control molecular weight and polymer architecture. To fully utilize the potential of ATRP as polymerization technique, the mechanism and the dynamics of the ATRP equilibrium must be well understood. In this thesis, various aspects of the ATRP process are explored through both laboratory experiments and computer modeling. Solvent effects, the limit of control and the use of iron as the mediator have been investigated. It was shown for copper mediated ATRP that the redox properties of the mediator and the polymerization properties were significantly affected by the solvent. As expected, the apparent rate constant (kpapp) increased with increasing activity of the mediator, but an upper limit was reached, where after kpapp was practically independent of the mediator potential. The degree of control deteriorated as the limit was approached. In the simulations, which were based on the thermodynamic properties of the ATRP equilibrium, the same trend of increasing kpapp with increasing mediator activity was seen and a maximum was also reached. The simulation results could be used to describe the limit of control. The maximum equilibrium constant for controlled ATRP was correlated to the propagation rate constant, which enables the design of controlled ATRP systems. Using iron compounds instead of copper compounds as mediators in ATRP is attractive from environmental aspects. Two systems with iron were investigated. Firstly, iron/EDTA was investigated as mediator as its redox properties are within a suitable range for controlled ATRP. The polymerization of styrene was heterogeneous, where the rate limiting step is the adsorption of the dormant species to the mediator surface. The polymerizations were not controlled and it is possible that they had some cationic character. In the second iron system, the intention was to investigate how different ligands affect the properties of an ATRP system with iron. Due to competitive coordination of the solvent, DMF, the redox and polymeri­zation properties were not significantly affected by the ligands. The differences between normal and reverse ATRP of MMA, such as the degree of control, were the result of different FeIII speciation in the two systems.<br>QC 20110406

Living/controlled radical polymerizations (L/CRPs) have been developed in the second half of the nineties and nowadays are among the most powerful and effective polymerization techniques for the preparation of advanced polymeric materials with well defined properties and high value. Atom Transfer Radical Polymerization (ATRP) has recorded the highest success in the field of L/CRP, thanks to its versatility and easiness of application. The first goal of this Ph.D. thesis is to understand and develop Cu-catalyzed ATRP through an electrochemical approach, with particular regard to the properties of the catalysts, initiators and propagating radicals, and the rationalization of the activation mechanism. Besides these fundamental aspects, a second important goal is to open a new way to enhance the control of the polymeric synthesis and allow the catalyst regeneration by means of electrochemical tools.<br>Le polimerizzazioni radicaliche controllate (Controlled radical polymerization, CRP) sono state sviluppate a partire dalla metà degli anni '90, e attualmente sono tra le più potenti ed efficaci metodologie di polimerizzazione per ottenere materiali polimerici avanzati con proprietà ben definite ed alto valore aggiunto. La polimerizzazione radicalica a trasferimento di atomo (Atom Transfer Radical Polymerization, ATRP) è la tecnica che ha riscontrato il maggior successo nel campo delle CRP grazie alla sua versatilità e facilità di applicazione. Scopo di questa tesi di dottorato è di fornire un contributo alla comprensione e allo sviluppo di ATRP catalizzata da rame attraverso un approccio elettrochimico, con particolare riguardo alle proprietà di: catalizzatore, specie dormiente e radicali propaganti, e alla comprensione del meccanismo di attivazione. Inoltre, un secondo importante obbiettivo è quello di sviluppare nuove metodologie elettrochimiche atte ad aumentare il controllo delle sintesi polimeriche e permettere la rigenerazione del catalizzatore.

Plusieurs mécanismes de polymérisation radicalaire contrôlée (PRC) sous irradiation lumineuse ont récemment été développés. Ces approches offrent potentiellement de nombreux avantages, en permettant notamment d’introduire dans le mécanisme des PRCs certaines caractéristiques propres aux photopolymérisations, tels que les contrôles spatial et temporel de la réaction. Les travaux de thèse présentés dans ce manuscrit s’inscrivent dans ce contexte, en ayant pour objectif le développement et l’étude d’un nouveau mécanisme de polymérisation radicalaire par transfert d’atome (ATRP) photocatalysée. Après une étude bibliographique présentant l’état de l’art dans le domaine des PRCs sous irradiation lumineuse (chapitre 1), un complexe de bis(1,10-phenanthroline) cuivre (I) (Cu(I)) est utilisé comme catalyseur pour la synthèse de poly(méthacrylate de méthyle)s bien définis par ATRP menée sous l’irradiation d’une lampe LED bleue de faible intensité (chapitre 2). Le mécanisme proposé implique la formation de l’état excité Cu(I)* à partir de Cu(I) sous irradiation, suivie de sa désactivation oxydative par les composés bromés, générant les espèces actives propagatrices et la forme désactivante du complexe Cu(II). Le cycle catalytique est ensuite complété par l’ajout de triethylamine comme agent réducteur permettant la régénération in situ de la forme activante Cu(I) du complexe et conduisant ainsi à une polymérisation plus rapide. Le méthacrylate de glycidyle est ensuite considéré comme comonomère jouant simultanément le rôle d’un agent réducteur (chapitre 3). Des copolymères fonctionnels bien définis, avec une distribution contrôlée de groupes latéraux époxydes, sont ainsi synthétisés. Enfin, le mécanisme d’ATRP photocatalysé est amélioré en développant une procédure permettant la génération in situ de la forme activante Cu(I) en partant d’un complexe Cu(II) stable en présence d’air (chapitre 4). Le mécanisme ainsi développé présente une bonne tolérance à la présence d’oxygène ou d’inhibiteur dans le milieu réactionnel. Les effets de plusieurs paramètres (intensité lumineuse, concentration en ligand et nature du solvant ou du contre-ion) sont étudiés, suggérant un échange de ligand photo-induit comme processus photochimique additionnel impliqué dans le mécanisme d’ATRP photocatalysé étudié<br>Several mechanisms of controlled radical polymerization (CRP) under light irradiation have been recently developed. These approaches offer potentially numerous advantages, enabling especially to introduce in the mechanism of CRPs some features characteristic of photopolymerizations, such as the spatial and temporal controls of the reaction. The PhD work presented in this manuscript comes in this framework, aiming at developing and studying a new mechanism of photocatalyzed atom transfer radical polymerization (ATRP). After a bibliographic study presenting the state-of-the-art in the domain of CRPs under light irradiation (chapter 1), a bis(1,10-phenanthroline) copper (I) complex (Cu(I)) is used as catalyst for the synthesis of well-defined poly(methyl methacrylate)s by ATRP carried out under the irradiation of a low intensity blue LED lamp (chapter 2). The proposed mechanism implies the formation of the excited state Cu(I)* from Cu(I) under irradiation, followed by its oxidative quenching by the brominated compounds, generating the growing active species and the deactivator form of the complex Cu(II). The catalytic cycle is then completed by the addition of triethylamine as a reducing agent enabling the in situ regeneration of the activator form of the complex Cu(I), therefore leading to a faster polymerization. Glycidyl methacrylate is then considered as a comonomer playing simultaneously the role of a reducing agent (chapter 3). Well-defined functional copolymers, with a controlled distribution of epoxide side groups, are thus synthesized. Finally, the photocatalyzed ATRP mechanism is improved by developing a procedure permitting the in situ generation of the activator Cu(I) starting directly from an air-stable Cu(II) complex (chapter 4). The mechanism developed in this way exhibits a good tolerance to the presence of oxygen or inhibitor in the reaction medium. The effects of several parameters (light intensity, ligand concentration and nature of the solvent or counter-ion) are studied, suggesting a photo-induced ligand-exchange as an additional photochemical process implied in the studied photocatalyzed ATRP mechanism

Atom transfer radical polymerization (ATRP) is one of the most broadly applied reversible deactivation radical polymerization (RDRP) technique that provide well-defined polymers with predetermined molecular weight (MW) and narrow molecular weight distribution (MWD). The functional polymers synthesized by ATRP showed a potential promise in the fields of biomedical applications such as smart drug delivery, tissue engineering, and diagnostic sensors. In general, conventional ATRP requires a large amount of transition metal catalysts (> 1000 parts per million (ppm) versus molar ratio of monomers) and removal of the residual catalysts is necessary for use of advanced materials in bio-applications. The advent of catalysts (re)generation from the oxidized transition metal/ligand catalysts allows for the use of ppm level of catalysts in an ATRP, and offers more environmentally benign and industrially favorable reaction conditions for the synthesis of polymers. This work mainly explores electrochemically controlled atom transfer radical polymerization (eATRP) with diminished catalysts conditions as one of many catalysts regeneration ATRP systems being examined in the past decade. This dissertation is composed of nine chapters. Chapter I reviews recent progress in electrochemically controlled chemical reaction and polymerization. Chapter II provides an in-depth study of eATRP and serves as a basis for the discussions in Chapter III on developing a simplified eATRP reaction (seATRP). Chapters II and III cover six appendices, which include related collaborations, explanations on catalysts development and characterization, polymerization mechanism, and evaluation of new polymerization procedures. Chapter IV and V address related aqueous eATRP techniques. Chapter IV details optimization of polymerization conditions for acrylamides and minimization of side reactions. Chapter V explores miniemulsion polymerization of n-butyl acrylate which requires optimization of aqueous-organic phase catalyst communication. Chapter VI addresses development of electrochemically mediated reversible addition-fragmentation chain transfer (eRAFT) polymerization of methyl methacrylate. Chapters VII to IX discuss the synthesis of copolymers with complex polymeric architectures, i.e., star polymers. Specifically in Chapter VII procedures for achieving high yield for the synthesis of stars by combining arm-first methods and eATRP to reduce initial intermolecular termination reactions. Chapter VII also contains an appendix on star synthesis by the core-first method via eATRP. Chapter VIII and IX elucidate applications of the functional star polymers. In Chapter VIII, the preparation and application of light induced crosslinkable star polymers in surface patterning are discussed and extended to biomedical applications. Lastly, Chapter IX encompasses temperature responsive surfaces, that were prepared by star polymers upon UV irradiation, as smart cell cultivate substrates.

The use of the radioisotope 14C in polymer chemistry has been reviewed, showing how it has been used to investigate the mechanistic aspects of free radical polymerizations, and the use of polymers in other scientific disciplines such as environmental, physical, chemical and medical sciences. An overview of the application of fluorescent spectroscopy to polymer chemistry is also reported. It covers the fundamentals of fluorescence chemistry, its application and the potential problems of the use of fluorescent labels in polymer chemistry. The application of radioisotopes to atom transfer radical polymerisation (ATRP) to investigate the fate of initiators used in the ATRP of 2-hydroxypropyl methacrylate (2- HPMA) is also reported. By using 14C radiolabelled initiators, radio thin layer chromatography (Radio TLC) and the liquid scintillation counting of fractions, collected from gel permeation chromatography (GPC), the fate of the initiating species where monitored during the polymerization of samples of 14C poly(2-HPMA), with degrees of polymerization of 10, 25 and 50 was assessed. GPC and Radio TLC, data showed that there was an under-utilisation of the initiator, 16% clearly observable at high monomer conversion (>97%), which could result in the initiation of new chains at monomer conversions of >90% and as late as 300 minutes after the polymerisation had started. These results contradict ATRP theory which states all initiator is consumed immediately at the commencement of the polymerization. 14C poly(2-HPMA) was also used to determine the efficiencies of the polymer purification methods, flash chromatography and precipitation. Although repeated precipitation increased fractionation, it was shown to be superior to flash chromatography in removing residual unreacted or terminated initiator. Finally, the possible effects of fluorescent labels on adsorption of low molecular weight 14C poly(DEAEMA) onto real surfaces (filter paper, photo graphic paper and hair) from aqueous solutions at pH=2 were investigated. Three low molecular weight samples of 14C poly(DEAEMA) were prepared by ATRP using 14C labelled initiators synthesized from alcohols of increasing hydrophobicity i.e. methyl, benzyl and 9-hydroxyfluorene (fluorescent label). The levels of adsorption were determined using phosphor imaging, oxidation of organic samples and liquid scintillation counting. Results indicated that differences in the chemistry of the polymer end groups can affect adsorption of the 14C poly(DEAEMA) and polymer assembly at the air/water interface. There was greater adsorption of polymers with a fluorescent end group. The increasing deposition was attributed to the increasing hydrophobicity of the polymer end group. Moreover, the controlled placement of one fluorescent label per polymer chain can influence the polymer’s properties, prompting the question, is the use of fluorescent groups to assess polymer behaviour and properties viable?

Despite the growing interest in heterogeneous polymerization catalysis, the majority of the polymerization catalysts used industrially are single-use entities that are left in the polymer product. Recoverable and recyclable polymerization catalysts have not reached the industrial utility of single-use catalysts because the catalyst and product separation have not become economical. The successful development of recyclable transition metal polymerization catalysts must take a rational design approach, hence academic and industrial researchers need to further expand the fundamental science and engineering of recyclable polymerization catalysis to gain an understanding of critical parameters that allow for the design of economically viable, recoverable solid polymerization catalysts. Unfortunately, the rapid development of Atom Transfer Radical Polymerization over the past 10 years has not resulted in its wide spread industrial practice. Numerous reports regarding the immobilization of transition metal ATRP catalysts, in attempts to increase its applicability, have extended the fundamentals of recyclable polymerization catalysis. However, for industrial viability, more research is required in the area of how the catalyst complex immobilization methodology and support structure affect the catalyst polymerization performance, regeneration, and recyclability. A comprehensive rational catalyst design approach of silica-immobilized ATRP catalyst was undertaken to answer these questions and are discussed here.

Thesis (Ph. D.)--Chemical and Biomolecular Engineering, Georgia Institute of Technology, 2005.<br>Jones, Christopher, Committee Chair ; Eckert, Charles, Committee Member ; Schork, Joseph, Committee Member ; Weck, Marcus, Committee Member ; Zhang, John, Committee Member. Includes bibliographical references.

In questo progetto è stata studiata la sintesi di copolimeri a blocchi poli(N-vinil caprolattame)-b-poli(vinil acetato) (PNVCL-b-PVAc) mediante Atom Transfer Radical Polymerization (ATRP). In visione di una futura produzione di questi materiali a livello industriale, è stato ritenuto interessante studiare questo processo utilizzando un solvente con alto valore di flash point, in particolare il polipropilen glicole Mn=1000g/mol (PPG-1000) (flash point 229°C). Inoltre, si è scelto di lavorare a temperature comprese tra 50 e 80°C, in modo da poter asportare il calore di reazione utilizzando semplicemente acqua non sottoraffreddata e ottenendo così una diminuzione dei costi di produzione. Sono quindi stati effettuati degli studi cinetici relativi alla sintesi dei due omopolimeri PNVCL e PVAc al fine di ottimizzare le condizione di sintesi ed ottenere un controllo sull’intero processo. In this work the synthesis of poly(N-vinyl caprolactam)-b-poly(vinyl acetate) (PNVCL-b-PVAc) block copolymers by Atom Transfer Radical Polymerization (ATRP) was studied. The process was carried out in presence of an high flash point solvent [polypropylene glycol Mn=1000g/mol (PPG-1000) (fp=229°C)] in order to attend to the environmental requirements of an industrial production and at temperature between 50 and 80°C with the aim to avoid the use of undercooled water for the heat removal, and hence reduce the production costs. Thus kinetic studies on the synthesis of PNVCL and PVAc homopolymers were performed in order to optimize the systems and obtain the control on the overall process.

work explores the application of Atom Transfer Radical Polymerization (ATRP) to improve various aspects of synthesizing well-defined porous polymer-based materials. The thesis specifically focuses on two particular classes on materials; mesoporous nitrogen-doped nanostructured carbons (N-doped nanocarbons) and polymerized high internal phase emulsions (polyHIPEs). The introductory chapter discusses, in great detail, reversible deactivation radical polymerization (RDRP) methods, including ATRP, that can be used to synthesize polyacrylonitrile-based precursors for the preparation N-doped nanocarbons and discusses their potential applications. The introduction chapter also details the requirements for formation of HIPEs and polyHIPEs, with a focus on the various hurdles that must be overcome for polyHIPEs to become commercially viable and widely applicable materials. Chapter 2 focuses on the synthesis of PAN-containing block copolymer (BCP) precursors by initiators for continuous activator regeneration (ICAR) and metal free (MF) ATRP, which allow for a significant reduction in the concentration of Cu-catalyst required for synthesis of well-defined BCPs; to 1 ppm in ICAR ATRP or no metal catalyst in MF ATRP. Chapter 3 discusses the synthesis of a range of PAN-based stars and characterization of carbon materials derived from these precursors. Chapter 4 discusses the synthesis and use of tetrazine cross-linked SiO2-g-Poly(4-cyanostyrene) as precursor for nitrogen-doped nanocarbons. The application of ATRP to prepare materials for use in HIPE systems and synthesize polyHIPEs was investigated in Chapter 5, where optimized conditions for activators generated by electron transfer (AGET) ATRP were developed to synthesize fully degradable polyHIPEs from commercially available monomers and cross-linker. Chapter 6 details the synthesis poly(ethylene oxide) and poly(n-butyl acrylate) mikto-arm stars that preferentially formed water in oil HIPEs and were able to stabilize water-in-xylene emulsions with star loading (vs. total emulsion) down to 0.005 wt% and water-in-styrene HIPEs down to 0.04 wt%. In a final step towards preparing a surfactant free stable polyHIPEs these mikto-arm stars were functionalized with reactive alkyl halide or vinyl moieties, so they could be incorporated into the polyHIPE network, as well as stabilize the HIPE, which is discussed in Chapter 7.

La polymérisation radicalaire par transfert d’atome (ATRP) est utilisée pour la synthèse de caoutchouc naturel greffé poly(méthacrylate de méthyle) (NR-g-PMMA). Des sites actifs du type bromoalkyle ont été introduits sur les chaînes macromoléculaires 1,4-polyisoprène du caoutchouc naturel (NR) en utilisant une procédure de modification chimique du NR conduite en deux étapes : époxydation partielle des insaturations carbone-carbone suivie de l’addition nucléophile d’un acide carboxylique fonctionnalisé bromoalkyle sur les cycles oxirane du caoutchouc naturel époxydé (ENR) obtenu. Le caoutchouc naturel fonctionnalisé bromoalkyle résultant a ensuite été utilisé en tant que macroamorceur pour amorcer l’ATRP du méthacrylate de méthyle (MMA) à partir des chaînes NR en variant les conditions de reaction. L’étude a été envisagée successivement avec le 4-méthyloct-4-ène (un molecule modèle de l’unité constitutive 1,4-polyisoprène du NR), un cis-1,4-polyisoprène de synthèse et le caoutchouc naturel. Dans une première partie, la faisabilité de la réaction de greffage est vérifiée en étudiant l’ATRP du MMA à partir de molécules modèles d’unités 1,4-polyisoprène fonctionnalisées bromoalkyle. Le 4-méthyloct-4-ène, modèle de l’unité 1,4-polyisoprène, est transformé en des modèles d’unités constitutives de caoutchouc naturel fonctionnalisé bromoalkyle via une procédure de modification chimique conduite en deux étapes : époxydation par action de l’acide m-chloroperbenzoïque (CPBA), suivie de l’addition de l’acide carboxylique fonctionnalisé bromoalkyle (acide 2-bromopropionique, A1, ou acide 2-bromo-2-méthylpropionique, A2) sur les cycles oxirane formés. L’addition de l’acide procède selon un mécanisme de substitution nucleophile SN2 avec fixation du groupe acide sur le carbone le moins substitué du cycle oxirane et est concurrencée par une réaction secondaire de réarrangement des cycles oxirane conduisant à la formation de deux alcools allyliques. Le rendement de l’addition dépend de l’acidité de l’acide carboxylique utilisé. Par la suite, l’aptitude de chacun des composés modèles, O-(2-hydroxy-2-méthyl-1-(n-propyl)pentyl)-2-bromopropionate et O-(2-hydroxy-2-méthyl-1-(n-propyl)pentyl)-2-bromoisobutyrate, à amorcer l’ATRP du MMA a été étudiée à 90°C dans le toluène, en utilisant CuBr complexé par un ligand polyamine comme système catalytique. Plusieurs ligands ont été testés : N-(n-octyl)-2-pyridylméthanimine (NOPMI), N-(n-octadecyl)-2-pyridylméthanimine (NODPMI) et 1,1,4,7,7-pentaméthyldiéthylènetriamine (PMDETA). Un bon contrôle des masses molaires moyennes en nombre (SECn,M) et indices de polymolécularité (PDI) a été obtenu avec le O-(2-hydroxy-2-méthyl-1-(n-propyl)pentyl)-2-bromoisobutyrate comme amorceur en présence du système catalytique CuBr/NOPMI. Dans la seconde partie, le cis-1,4-polyisoprène de synthèse (PI) est transformé en un macroamorceur de type polyisoprène fonctionnalisé bromoalkyle (PI-Br) en utilisant une procédure de modification chimique en deux étapes similaire à celle utilisée pour la synthèse de l’amorceur modèle. PI a été partiellement époxydé à l’aide du CPBA dans le dichlorométhane, et le PI époxydé (EPI) obtenu a ensuite été soumis à l’action de A2. L’addition de l’acide se fait selon un mécanisme de substitution nucléophile SN2 avec fixation du groupe acide sur le carbone le moins substitué du cycle oxirane (addition de type β) et est concurrencée par une réaction secondaire de réarrangement des oxiranes conduisant à des structures de type alcool allylique externe. Les SECn,M et PDI des greffons PMMA ont été déterminés par Chromatographie d’Exclusion Stérique après séparation du squelette PI par hydrolyse des liaisons ester par action de l’acide trifluoroacétique. Une cinétique du premier ordre par rapport au monomère et une augmentation linéaire de SECn,M avec la conversion du MMA sont observées en utilisant le Cu(I)Br complexé par les ligands bidentate (NOPMI et NODPMI) et tridentate (PMDETA), comme systèmes catalytiques. Avec les ligands bidentate, le PDI des greffons est cependant mieux contrôlé. Il convient en outre de préciser que le contrôle deSECn,M et du PDI des greffons PMMA est très affecté par l’augmentation du taux d’unités constitutives fonctionnalisées bromoalkyle au sein du PI-Br. Dans la dernière partie, NR est utilisé comme matériau de départ. Il est partiellement époxydé en ENR en milieu latex par action de l’acide performique généré in-situ par réaction entre l’acide formique et le peroxyde d’hydrogène, puis l’ENR est transformé en NR fonctionnalisé bromoalkyle (NR-Br) par addition nucléophile de A2 sur les cycles oxirane. L’addition de l’acide est similaire à celle observée lors des études réalisées précédemment avec le 4-méthyloct-4-ène et le PI. Le NR-Br résultant a ensuite été utilisé pour amorcer l’ATRP du MMA à partir des chaînes de NR, respectivement en solution dans le toluène et en milieu dispersé aqueux. L’AGET-ATRP a également été envisagée en milieu dispersé aqueux pour étudier l’influence de l’eau en vue de futures études de greffages par ATRP en milieu latex. En mode ATRP normale en milieu toluène, les réactions de terminaison par recombinaison entre les extrémités radicalaires actives des greffons PMMA sont défavorisées lorsque la concentration en MMA est diminuée de 30 % à 10 % en poids. Les PDIs des greffons varient entre 1,7 (pour une conversion en MMA de 8,1 %) à 2,0 (pour une conversion de 52 %). Un meilleur contrôle des SECn,M et PDI des greffons est obtenu par ATRP normale en milieu dispersé aqueux, plus spécialement lorsque le CuBr est complexé par le NODPMI. Dans ces conditions, les PDIs des greffons PMMA sont faibles (1. 5 lorsque le taux de conversion du MMA est peu élevé). En mode AGET-ATRP en milieu dispersé aqueux, il a été mis en évidence que l’efficacité du greffage est affectée par la concentration en acide ascorbique utilisé en tant qu’agent réducteur. Les structures chimiques obtained ont été caractérisées par FT-IR, et RMN 1H et 13C. Les propriétés thermiques des NR-g-PMMA synthétisés ont été étudiées par Analyse Calorimétrique Différentielle (DSC). La présence de deux Tgs, à environ -14°C et 99°C, sur les courbes DSC des NR-g-PMMAs dont les teneurs en poids en PMMA sont supérieures à 65 %, montre que ces matériaux adoptent une morphologie biphasée<br>Atom Transfer Radical Polymerization (ATRP) technique was applied for synthesis of natural rubber-grafted-poly(methyl methacrylate) (NR-g-PMMA). Active sites on macromolecular chains of NR were created by fixation of bromoalkyl groups via a two-step chemical modification: partial epoxidation on unsaturated carbon-carbon bonds, followed by nucleophilic addition of a bromoalkyl-functionalized carboxylic acid on the oxirane rings of the epoxidized natural rubber (ENR) obtained. The resulting bromoalkyl-functionalized rubber was then used as macroinitiator to initiate the ATRP of methyl methacrylate (MMA) from NR chains by varying reaction conditions. The study was successively envisaged with 4-methyloct-4-ene (a model molecule of NR repeating unit), a synthetic cis-1,4-polyisoprene, and natural rubber. In the first part, the feasibility of the grafting reaction is verified by studying the ATRP of MMA from model molecules of bromoalkyl-functionalized 1,4-polyisoprene units. The model of the 1,4-polysisoprene unit, 4-methyloct-4-ene, is transformed in various models of bromoalkyl-functionalized 1,4-polyisoprene units via a chemical modification procedure carried out in two-steps: epoxidation performed with m-chloroperbenzoic acid (CPBA) followed by the addition of the bromoalkyl-functionalized carboxylic acid (2-bromopropionic acid, A1, or 2-bromo-2-methylpropionic acid, A2) on the oxirane ring formed. The addition of the acid occurs according to an SN2 mechanism with fixation of the acid group on the less substituted carbon of the oxirane ring and is competed with a secondary reaction of rearrangement of oxirane ring, leading to the formation of two allyl alcohols. The yield of the addition depends on the acidity of the carboxylic acid used. Afterwards, resulting O-(2-hydroxy-2-methyl-1-(n-propyl)pentyl)-2-bromopropionate and O-(2-hydroxy-2-methyl-1-(n-propyl)pentyl)-2-bromoisobutyrate, were used to initiate the ATRP of MMA at 90°C in toluene using Cu(I)Br complexed with a polyamine ligand. Several ligands were tested: N-(n-octyl)-2-pyridylmethanimine (NOPMI), N-(n-octadecyl)-2-pyridylmethanimine (NODPMI), and 1,1,4,7,7-pentamethyldiethylenetriamine (PMDETA). A good control of molecular weights (SECn,M) and polydispersity indexes (PDI) were obtained with O-(2-hydroxy-2-methyl-1-(n-propyl)pentyl)-2-bromoisobutyrate as the initiator in presence of CuBr/NOPMI as catalytic system. In the second part, the synthetic cis-1,4-polyisoprene (PI) is transformed into a bromoalkyl-functionalized polyisoprene (PI-Br) macroinitiator using a two-step chemical modification procedure similar to that used for synthesis of the model. PI was partially epoxidized using CPBA in dichloromethane, and then the epoxidized PI (EPI) obtained was reacted with A2. The addition of the acid occurs according to an SN2 mechanism with fixation of the acid group on the less substituted carbon of the oxirane ring (β-addition) and is competed with rearrangement reactions of oxirane rings, leading to external allyl alcohol. SECn,M and PDI of PMMA grafts were determined by Size Exclusion Chromatography after separation from the PI backbone by hydrolysis of the ester bond using trifluoroacetic acid. An internal first order kinetic plot with respect to monomer and an increase of SECn,M with MMA conversion were observed using Cu(I)Br complexed with bidentate (NOPMI and NODPMI) and tridentate (PMDETA) ligands, as catalytic systems. With bidentate ligands, the PDI of grafts is better controlled. Moreover, the control of SECn,M and PDI of PMMA grafts was affected by increasing the degree of initiating units in PI-Br. In the last part, NR is used as a starting material. It was partially epoxidized in ENR in latex medium by reaction with performic acid generated in-situ from formic acid and hydrogen peroxide, and then ENR was transformed in bromoalkyl-functionalized NR (NR-Br) by nucleophilic addition of A2 on the oxirane rings. The addition of the acid is similar to that observed during the studies performed with 4-methyloct-4-ene and PI. Resulting NR-Br was then used to initiate the graft polymerization of MMA from NR chains using normal ATRP in toluene solution and in aqueous dispersed medium, respectively. AGET-ATRP was also considered in aqueous dispersed medium to study the effect of water for further ATRP graft copolymerization studies with NR latices. By normal ATRP in toluene solution, the termination reactions by recombination decreased as MMA concentration deceased, from 30 wt% to 10 wt%. PDIs of PMMA grafts vary in range from 1. 7 (at 8. 1 % MMA conversion) to 2. 0 (at 52. 0 % MMA conversion). A better control of the SECn,M and PDI of PMMA grafts was obtained by using normal ATRP in aqueous dispersed medium, more especially when CuBr was complexed with NODPMI. In these conditions, PDIs of PMMA grafts were low (closed to 1. 5 at low MMA conversion). In AGET-ATRP performed in aqueous dispersed medium, it was shown that the efficiency of graft copolymerization is affected by the concentration in ascorbic acid used as reducing agent. The chemical structures obtained were characterized by FT-IR, and by 1H and 13C NMR. The thermal properties of the graft copolymers synthesized were studied by Differential Scanning Calorimetry (DSC). The presence of two Tgs, at about -14°C and 99°C respectively, on the DSC curves when the amounts of PMMA in NR-g-PMMAs are higher than 65 wt%, shows that these materials adopt a biphasic morphology

The aim of this thesis is to push forward the synthesis of well-defined materials containing polar monomers. The ATRP of polar monomers was investigated with the aim to obtain living and well-defined materials. Block copolymers with pre-determinable composition and unimodal distribution of molecular weight were synthesized. Furthermore, the Atom Transfer Radical Co-Polymerization of NVCL and NVP with non-polar monomers was investigated with the aim to obtain amphiphilic material with tunable polarity. The ATRP of vinyl acetate (VAc), which was poorly optimized, was studied trying to obtain poly(VAc) with low polydispersity (<1.25), pre-determinable molecular weight and living character. The optimization of the ATRP of VAc and the synthesis of several block copolymers, synthesized in presence of different experimental conditions, can significantly expand the field of materials and applications of poly(VAc) and poly(vinyl alcohol)-based products. Moreover, the synthesis of pH and temperature polymers was investigated with the aim to obtain products suitable for the development of drug-delivery systems which can be applied in anti-cancer applications. For this purpose Pluronic F127, which is thermosensitive, and poly(ethylene glycol)s were modified with pH poly[2-(N,N-dimethylamino)ethyl methacrylate] (PDMAEMA), poly[2-(N,N-diethylamino)ethyl methacrylate] (PDEAEMA) and poly[2-(N,N-diisopropylamino)ethyl methacrylate] (PDIAEMA). The methacrylic moieties have different pKa, and they give to the synthesized materials the desired pH responsiveness. The gelation behavior of the obtained products was investigated by rheological measurements; the dimension of the polymeric aggregates in water solutions at different pH was studied by DLS and the drug-incorporation as a function of pH was determined in systems with stable pH and in systems in which the pH was decreased progressively. All the cited investigation allowed to well-characterized the behavior and the structure of polymeric aggregates in water solution and they also allowed to determine their pH and temperature responsiveness.

The aim of this thesis is to push forward the synthesis of well-defined materials containing polar monomers. The ATRP of polar monomers was investigated with the aim to obtain living and well-defined materials. Block copolymers with pre-determinable composition and unimodal distribution of molecular weight were synthesized. Furthermore, the Atom Transfer Radical Co-Polymerization of NVCL and NVP with non-polar monomers was investigated with the aim to obtain amphiphilic material with tunable polarity. The ATRP of vinyl acetate (VAc), which was poorly optimized, was studied trying to obtain poly(VAc) with low polydispersity (<1.25), pre-determinable molecular weight and living character. The optimization of the ATRP of VAc and the synthesis of several block copolymers, synthesized in presence of different experimental conditions, can significantly expand the field of materials and applications of poly(VAc) and poly(vinyl alcohol)-based products. Moreover, the synthesis of pH and temperature polymers was investigated with the aim to obtain products suitable for the development of drug-delivery systems which can be applied in anti-cancer applications. For this purpose Pluronic F127, which is thermosensitive, and poly(ethylene glycol)s were modified with pH poly[2-(N,N-dimethylamino)ethyl methacrylate] (PDMAEMA), poly[2-(N,N-diethylamino)ethyl methacrylate] (PDEAEMA) and poly[2-(N,N-diisopropylamino)ethyl methacrylate] (PDIAEMA). The methacrylic moieties have different pKa, and they give to the synthesized materials the desired pH responsiveness. The gelation behavior of the obtained products was investigated by rheological measurements; the dimension of the polymeric aggregates in water solutions at different pH was studied by DLS and the drug-incorporation as a function of pH was determined in systems with stable pH and in systems in which the pH was decreased progressively. All the cited investigation allowed to well-characterized the behavior and the structure of polymeric aggregates in water solution and they also allowed to determine their pH and temperature responsiveness.

In this study, ethyl methacrylate was polymerized by free radical polymerization at 600C, 700C, 800C at open atmosphere<br>atom transfer radical polymerization, (ATRP), at 800C in vacuum and in gamma irradiation in vacuum. The polymer obtained was white, hard material. The kinetic curves for free radical polymerization and ATRP by gamma radiation were S-type. However, the curve for polymerization by gamma irradiation raises more smoothly. For ATRP by thermal initiation gives a lineer change of conversion with time. It was observed that the molecular weight can be controlled and low molecular weight polymer could be obtained by ATRP method. The characterization of polymers were made by FTIR, DSC, 1H and 13C NMR techniques.

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.

Thesis (MSc)--Stellenbosch University, 2001<br>ENGLISH ABSTRACT: The effect of various organic reducing agents, in the. form of monosaccharide reducing sugars, on the rate of atom transfer radical polymerization (ATRP) of n-butyl methacrylate and methyl methacrylate is reported in this study. The addition of the reducing sugars has a positive effect on the rate of ATRP. Up to 100% increase in the rate of polymerization was recorded, in some cases. These organic reducing agents have little effect on the molecular weight and molecular weight distribution of the polyin-butyl methacrylate) and polydispersity indexes remain well below 1.2. The molecular weight of the poly(methyl methacrylate), when glucose and galactose are added to the reaction mixture, compares well with the theoretical expected values. An explanation for these observations is the ability of the reducing sugars to reduce part of the Cu(II) species, that serves to deactivate the growing radicals, to Cu(I), thereby ensuring a shift in the equilibrium between active and dormant chains in the direction of the former and a resulting increase in the rate of polymerization. uvNIS spectroscopy and cyclic voltammetry were used to investigate the mechanism behind the polymerization rate enhancement.<br>AFRIKAANSE OPSOMMING: In hierdie studie word die effek van verskeie organiese reduseermiddels, in die vorm van monosakkaried reduserende suikers, op die tempo van polimerisasie van ATRP gerapporteer. Hierdie reduserende suikers het 'n positiewe effek op die polimerisasie tempo. In sommige gevalle word 'n toename van 100% in die polimerisasie tempo waargeneem. Die organiese reduseermiddels het 'n minimale effek op die molekulere massa en molekulere massa verspreiding (in meeste gevalle minder as 1.2) van die poly(n-butiel metakrielaat). In die geval van die poly(metiel metakrielaat), wanneer glukose en galaktose by die reaksie mengsel gevoeg word, stem die molekulere massas goed ooreen met die teoreties voorspelde molekulere massas. Die waargenome toename in die polimerisasie tempo kan toegeskryf word aan die vermoe van die reduserende suikers om die Cu(II), wat dien om die groeiende radikale te deaktiveer, gedeeltelik te reduseer na Cu(l). Hierdeur word verseker dat die ewewig tussen die aktiewe en dormante kettings in die rigting van die eersgenoemde verskuif word, wat dus aanleiding gee tot 'n toename in die polimerisasie tempo. Ultraviolet spektroskopie en sikliese voltammetrie is ook gebruik om lig te werp op die meganisme agter die toename in die tempo van polimerisasie.

Many pathogenic bacteria can enter phagocytic cells and replicate in them, and these intracellular bacteria are difficult to treat because the recommended antibiotics do not transport into the cells efficiently. Examples include food-borne bacteria such as Salmonella and Listeria as well as more toxic bacteria such as Brucella and the Mycobacteria that lead to tuberculosis. Current treatments utilize aminoglycoside antibiotics that are polar and positively charged and such drugs do not enter the cells in sufficient concentrations to eradicate the intracellular infections. We have developed core-shell polymeric drug delivery vehicles containing gentamicin to potentially overcome this challenge. Pentablock and diblock copolymers comprised of amphiphilic nonionic polyether blocks and anionic poly(sodium acrylate) blocks have been complexed with the cationic aminoglycoside gentamicin. The electrostatic interaction between the anionic polyacrylates and the cationic aminoglycosides form the cores of the nanoplexes, while the amphiphilic nature of the polyethers stabilize their dispersion in physiological media. The amphiphilic nature of the polyethers in the outer shell aid in interaction of the nanoplexes with extra- and intra-cellular components and help to protect the electrostatic core from any physiological media. This thesis investigates the electrostatic cooperativity between the anionic polyacrylates and cationic aminoglycosides and evaluated the release rates of gentamicin as a function of pH.<br>Master of Science

In the present thesis, we propose a modification of silicone surfaces using the controlled deposition of amphiphilic block copolymers from aqueous colloidal dispersions. The surface modifiers are based on poly(dimethylsiloxane) (PDMS) as the hydrophobic part, in order to allow a good compatibility with PDMS artefacts, and poly(glycerol monomethacrylate) (PGMMA) as the hydrophilic block, since this polymer has demonstrated good biocompatibility and low cell attachment. The hydroxyl groups present on PGMMA offer the possibility of further surface functionalization. We have demonstrated the convenience of preparing well-defined amphiphilic block copolymers of PDMS and PGMMA (which we refer to as Sil-GMMA polymers) via atom transfer radical polymerization using a protection/deprotection route (i.e. the silylation of GMMA alcohols groups). Depending on the ratio between hydrophobic and hydrophilic blocks, Sil-GMMA copolymers can self-assemble into micellar and other colloidal structures. Diffusion ordered nuclear magnetic resonance experiments have shown that those micelles did not interact with albumin, suggesting a “stealth” behaviour. Once a library of Sil-GMMA polymers with various block ratio was prepared, the adsorption of Sil-GMMA colloidal dispersions in water/ethanol on PDMS surfaces by simple physisorption was studied. As expected, high PDMS content favoured Sil-GMMA adsorption on silicone surfaces. The presence of our surface modifiers on silicone surfaces was confirmed by a decrease in water contact angle and spectroscopy techniques. We have shown that the surface coatings were stable upon storage in water. Additionally, fibrinogen adsorption was decreased by Sil-GMMA adsorption while albumin adsorption appeared to increase. The preparation of surfaces repellent to fibrinogen and interacting with a “passivating” protein such as albumin is promising. At the same time, this thesis also reports preliminary investigations on the use of enzymes in order to incorporate new functionality to GMMA containing polymers. Although enzymatic activity was observed when using PGMMA instead of glycerol with two different enzymes (glycerol kinase and glycerol dehydrogenase), PGMMA conversions were always low (< 2%).