No / Crystallization of an isotactic polypropylene (iPP) homopolymer and two propylene/ethylene random copolymers (RACO), induced by high-stress shear, was studied using in situ synchrotron wide-angle X-ray diffraction (WAXD) at 137 °C. The “depth sectioning” method (Fernandez-Ballester Journal of Rheology 2009, 53 (5), 1229−1254) was applied in order to isolate the contributions of different layers in the stress gradient direction and to relate specific structural evolution to the corresponding local stress. This approach gives quantitative results in terms of the specific length of fibrillar nuclei as a function of the applied stress. As expected, crystallization becomes faster with increasing stress—from the inner to the outer layer—for all three materials. Stress-induced crystallization in a RACO with 7.3 mol % ethylene content was triggered at only 1 °C below its nominal melting temperature. The comparison of iPP and RACO’s with 3.4 and 7.3 mol % ethylene monomer reveals the effect of ethylene defects on high-stress shear induced crystallization at 137 °C. It is found that, for a given applied stress, the specific nuclei length formed by flow increases with ethylene content—which is attributed to a greater high molecular weight tail. However, the linear growth rate is significantly reduced by the presence of ethylene comonomers and it is found that this effect dominates the overall crystallization kinetics. Finally, a time lag is found between development of parent lamellae and the emergence of daughter lamellae, consistent with the concept of daughter lamellae nucleated by homoepitaxy on the lateral faces of existing parent lamellae.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Polydimethylsiloxane–polyester (PDMS-PES) copolymers produce materials which have enhanced properties and take advantage of the unique properties of the two very dissimilar components. The dissimilar nature of the components results in these types of materials typically having complex morphologies in the solid state as a result of phase segregation. When the polyester component is crystallisable, an even richer variation in morphology can be expected. The chain structure of the copolymer in terms of the distribution of the various segments along the chain and the variation in the composition also has a dramatic impact on the solid state morphology. In this study, two different types of polyesters were used to synthesise five series of PDMS-PES segmented copolymers and one series of PDMS-PES branched copolymer. The two polyester segments selected were polybutyleneadipate (PBA) and polybuthylenecyclohexancarboxylate (PBCH). The copolymers were synthesised via polycondensation in the melt state. Insights on many variations in the PDMS-PES copolymer synthesis are given. The copolymer series synthesized gave systematic series where the influence of the polyester type, chain architecture, bulk composition, block length, crystallinity and processing condition on the bulk and surface morphology could be studied. The remarkable variations in the properties of the copolymer were attributed to the differences in the copolymers morphology in terms of the microphase segregation, crystallization and the free volume properties. These variations were also found to alter the nature of the surface compositions and the related surface properties. Multiphase morphology exhibited in all the PDMS-PES copolymers and the type of morphology observed was dependent on PDMS contents, PDMS segment length and the degree of branching. Three types of morphology were observed: spherical micro-domains of PDMS in a matrix of PES, bicontinuous double diamond type morphology, and spherical micro-domains of PES in a matrix of PDMS. Spherical domains of the PDMS were also observed for low PDMS content copolymers between the crystalline polyester lamellae. The complexity of the PDMS-PBCH copolymer morphology was further investigated, using an extensive set of experimental data that has been drawn together with using positron annihilation lifetime spectroscopy (PALS) and developing and applying a new type of hyphenated technique between fractionation (chromatography) and microscopy (atomic force microscopy) techniques. The outcome has provided a unique perspective regarding the complexity of the PDMS-PBCH copolymer morphology, which is believed to provide basis for a theoretical structure-properties relationship in this fascinating class of thermoplastic material. / AFRIKAANSE OPSOMMING: Polidimetielsiloksaan–poliëster (PDMS–PES) kopolimere lewer verbindings met goeie eienskappe en trek voordeel uit die unieke eienskappe van die twee baie verskillende komponente. Aangesien die aard van hierdie twee verbindings baie verskil het hulle ‘n gekompliseerde morfologie in die vastetoestand as gevolg van faseskeiding. Wanneer die poliëster komponent kristalliseerbaar is kan ‘n nog ryker variasie in morfologie verwag word. Die kettingstruktuur van die kopolimere in terme van die verspreiding van die verskillende segmente al langs die ketting en die variasie in samestelling, het ook ‘n groot invloed op die vastetoestandmorfologie. In hierdie studie is twee verskillende tipes poliëster gebruik om vyf reekse PDMS–PES gesegmenteerde kopolimere en een reeks vertakte PDMS–PES kopolimere te berei. Die twee poliëstersegmente is polibutileenadipaat (PBA) en polibutileensikloheksaankarboksilaat (PBCH). Die kopolimere is berei deur middel van polikondensasie in die smeltfase. Inligting aangaande verskeie faktore in the bereiding van die PDMS–PES kopolimere is ingewin. Die reekse kopolimere wat berei is, het dit moontlik gemaak om die invloed van die tipe poliëster, kettingargitektuur, grootmaatsamestelling, bloklengte, kristalliniteit en reaksiekondisies op die oppervlakte en interne morfologie te bestudeer. Die opmerklike verskille in the eienskappe van die kopolimere word toegeskryf aan die verskille in die kopolimeermorfologie in terme van die mikrofaseskeiding, kristalliniteit en vryevolume eienskappe. Hierdie verskille het ook veranderings in die oppervlakte samestellings en verwante oppervlakte eienskappe teweeggebring. Multifase morfologie, in alle PDMS–PES kopolimere en die tipe morfologie wat waargeneem is, is afhanklik van die PDMS inhoud, die PDMS segmentlengte en die graad van vertakking. Drie tipes morfologie is waargeneem: sferiese mikro-gebiede van PDMS in ‘n PES matriks, ‘n bikontinueerlike dubbele-diamant tipe en sferiese mikro-gebiede van PES in ‘n PDMS matriks. Sferiese gebiede van die PDMS is ook waargeneem in kopolimere met ‘n lae PDMS inhoud tussen die kristallyne poliëster lae. Die kompleksiteit van die PDMS–PBCH kopolimeermorfologie is verder ondersoek deur gebruik te maak van ‘n wye reeks eksperimentele data afkomstig van positronvernietigingsleeftydspektroskopie (PALS), gevolg deur die ontwikkeling en toepassing van ‘n nuwe soort gekoppelde tegniek – tussen fraksionering (chromatografie) en mikroskopie (atoomkragmikroskopie) tegnieke. Die resultate het ‘n unieke perspektief gegee wat betref die kompleksiteit van die PDMS–PBCH kopolimeermorfologie en dien as ‘n basis vir die teoretiese struktuur–eienskapverwantskap van hierdie interessante klas termoplastiese materiale.

The synthesis and preliminary optoelectronic properties of a series of donor-acceptor (DA) type polymers differing by the acceptor units in the polymer backbone were investigated. Polymers CoP1, CoP2 and CoP3 were designed to yield alternating DA segments with randomly distributed different acceptor units along polymer backbone. The combination of neutral state red colored and neutral state green colored materials resulted in different neutral state colors with respect to their additional acceptor unit. 5,8-Dibromo-2,3-bis(4-tert-butylphenyl) quinoxaline, 5,8-dibromo-2,3-di(thiophen-2-yl)quinoxaline and 4,7-dibromobenzo[c][1,2,5]selenadiazole units were perceived as additional acceptor units and these constituents were combined with the 4,7-dibromo-2-dodecyl-2H-benzo[d][1,2,3]triazole unit and the 2,5-bis(tributylstannyl)thiophene moiety via Stille coupling. The resultant donor acceptor type random copolymers indicated that possessing 5,8-dibromo-2,3-di(thiophen-2-yl)quinoxaline as an extra electron deficient with 4,7-dibromo-2-dodecyl-2H-benzo[d][1,2,3]triazole unit on the same polymer backbone originated a neutral state black colored copolymer along with spanning the entire visible spectrum.

Hydrophilic/hydrophobic block copolymers as proton exchange membranes (PEMs) has become an emerging area of research in recent years. Three series of hydrophilic/hydrophobic, fluorinated/sulfonated multiblock copolymers were synthesized and characterized in this thesis. These copolymers were obtained through moderate temperature (~100°C) coupling reactions, which minimize the ether-ether interchanges between hydrophobic and hydrophilic telechelic oligomers via a nucleophilic aromatic substitution mechanism. The hydrophilic blocks were based on the nucleophilic step polymerization of 3,3′-disulfonated, 4,4′-dichlorodiphenyl sulfone with an excess 4,4′-biphenol to afford phenoxide endgroups. The hydrophobic (fluorinated) blocks were largely based on decafluoro biphenyl (excess) and various bisphenols. The copolymers were obtained in high molecular weights and were solvent cast into tough membranes, which had nanophase separated hydrophilic and hydrophobic regions. The performance and structure-property relationships of these materials were studied and compared to random copolymer systems. NMR results supported that the multiblock sequence had been achieved. They displayed superior proton conductivity, due to the ionic proton conducting channels formed through the self-assembly of the sulfonated blocks. The nano-phase separated morphologies of the copolymer membranes were studied and confirmed by atomic force microscopy. Through control of a variety of parameters, including ion exchange capacity and sequence lengths, performances as high, or even higher than those of the state-of-the-art PEM, Nafion, were achieved. / Ph. D.

Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Heterophasic ethylene-propylene copolymers, also known as impact polypropylene (PP) copolymers (IPCs) or heterophasic copolymers (HECOs), are a unique group of polyolefins produced through the copolymerisation of ethylene and propylene, with the aim of improving the impact properties of the PP homopolymer at low temperatures. Therefore, this polymer comprises of a PP homopolymer matrix with a dispersed rubbery copolymer phase. Due to their unique properties, HECO polymers have become commercially important materials, with a wide range of applications. Therefore a fundamental understanding of the processes and chemistry that affects their final macroscopic properties needs to be expanded. The main focus of this investigation was to understand why specific organic peroxides influence or interact differently with the various phases of HECO polymers, in order to utilize their properties to obtain HECO polymers with optimal and desired properties. Two HECO polymers with different ethylene contents were fractionated into three fractions (30, 100 and 130 °C), using preparative temperature rising elution fractionation (P-TREF). Each individual TREF fraction was degraded with two different types of organic peroxides, and then characterised using four different analytical tools. The changes in the molecular structures of the different fractions were investigated by Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The changes in comonomer sequence distributions were investigated by carbon 13 nuclear magnetic resonance spectroscopy (13C-NMR). Moreover, the degradation of the different fractions was investigated by high temperature size exclusion chromatography (HT-SEC). The investigation showed that the HECO polymers with different ethylene contents were uniquely altered. It was evident that the ethylene content influenced the degradation behaviour of the HECO polymers. The ability of the peroxide to affect certain regions of the HECO polymer more than others is highly dependent upon its miscibility with certain regions of the HECO polymers. The “visbreaking” efficiency of a specific organic peroxide appears to be primarily dependent on the number of “peroxy” groups it contains in its molecular structure. Stellenbosch University https://scholar.sun.ac.za / AFRIKAANSE OPSOMMING: Heterofase etileen-propileen ko-polimere, ook bekend as impak PP ko-polimere (IPCS) of heterofase ko-polimere (HECO), is 'n unieke groep poliolefiene geproduseer deur die ko-polimerisasie van etileen en propileen, met die doel op die verbetering in die impak eienskappe van die PP homopolimeer by lae temperature. Hierdie polimeer bestaan dus uit 'n PP homopolimeer matriks met 'n verspreide rubberagtige ko-polimeer fase. As gevolg van hul unieke eienskappe, is HECO polimere van kommersiële belang, met 'n wye verskeidenheid van toepassings. 'n Fundamentele begrip van die prosesse en chemie wat die finale makroskopiese eienskappe beïnvloed moet dus uitgebrei word. Die hooffokus van hierdie ondersoek was om te verstaan waarom spesifieke organiese peroksiede verskillende invloede en interaksies met die verskillende fases van HECO polimere het, om sodoende van hul eienskappe gebruik te maak om HECO polimere te verkry met optimale en gewenste eienskappe. Twee HECO polimere met verskillende etileen inhoud was gefraksioneer in drie fraksies (30, 100 en 130 °C), met behulp van preparatiewe temperatuur styging eluering fraksionering (P-TREF). Elke individuele TREF fraksie was gedegradeer met twee verskillende tipes organiese peroksiede en daarna gekarakteriseer deur vier verskillende analitiese metodes. Die veranderinge in molekulêre strukture van die verskillende fraksies was geondersoek met behulp van Fourier transform infrarooi spektroskopie (FTIR) en differensiële skandering kalorimetrie (DSC). Die veranderinge in ko-monomeer volgorde distribusie was bestudeer deur middel van kern magnetiese resonans spektroskopie (KMR). Verder was die degradasie van die verskillende fraksies met behulp van hoë temperatuur grootte uitsluitingschromatografie (HT-SEC) bestudeer. Die ondersoek het getoon dat die HECO polimere met verskillende etileen inhoud uniek gedegradeer was. Dus is dit duidelik genoeg dat die etileen inhoud die degradasie gedrag van die HECO polimere beïnvloed het. Die vermoë van die peroksied om sekere areas van die HECO polimeer meer as ander te beïnvloed is hoogs afhanklik van die mengbaarheid met sekere areas van die HECO polimere. Die "visbreking" doeltreffendheid van 'n spesifieke organiese peroksiede is meestal afhanklik van die aantal "peroksie" groepe in die molekulêre struktuur.

In 1980’s a new class of material named as dendrimer became popular both in the field of polymer science and engineering. Dendrimer is an example of symmetric, highly branched three dimensional globular nano-object. It possess several interesting physical and chemical properties like low solution and melt-viscosity, lower intermolecular chain entanglement, large number of end groups placed at the molecular periphery, relatively high solubility with respect to their linear counterpart. In order to get this perfectly branched structure, one has to go through the tedious multistep synthetic approach, repetitive chromatographic purification and protection-deprotection strategies in every step; all of which limits the large scale production and thus commercialization. On the other hand, hyperbranched polymer, a highly branched analogue of dendritic polymer with few defects in their branching architecture, which can be prepared in a single step, show similar physical and chemical properties as that of dendrimer. Polymerization of AB2 monomer is one of the well established method to generate hyperbranched polymer which upon polymerization, generates plenty of ‘B ’groups at the periphery along with a single ‘A’ group as a focal point in the resulting hyperbranched polymer as shown in Figure 1. From the structural point of view, hyperbranched polymers consist of three distinctly different compartments such as periphery, interior and a (single) focal point. During the past decade our lab have developed a novel melt trans-etherification process to generate polyethers and have utilized to access to a wide variety of hyperbranched structures. One of the challenges we addressed is to selectively functionalize the periphery of the hyperbranched polymer during the polymerization process. Polycondensation of ‘AB2’ monomer is not sufficient enough to generate a wide variety of hyperbranched polymer as the periphery of hyperbranched polymer is limited to the ‘B’ functional group unless it could be modified via ‘post-polymerization modifications’. Copolymerization of ‘AB2’ monomer with stoichiometric amount of ‘A-R’ monomer should result in hyperbranched polymer decorated with ‘R’ groups in the periphery that can be prepared in a single step. One of the prerequisite in the ‘AB2+A-R’ approach is that the comonomer ‘A-R’ should have silent ‘R’ group which does not interfere during the polymerization. During the copolymerization process with stoichiometric amount of ‘A-R’ monomer, ‘AB2’ monomer having one equivalent excess of ‘B’ can react with the ‘A’ group from ‘A-R’ monomer eventually generating the hyperbranched structure with peripheral ‘R’ groups. By appropriately choosing the ‘R’ group, one can access a wide class of hyperbranched polymer with the required functionality. Further by having a reactive ‘R’ group that is not participating in polymerization can act as a handle for post-polymerization modifications. For instance, copolymerization of 1-(6-Hydroxyhexyloxy)-3,5-bis(methoxymethyl)-2,4,6-trimethylbenzene (Hydroxy as ‘A’ and methoxy as ‘B’) and 6-bromo-1-hexanol where ‘OH’ and ‘-(CH2)6Br’ is ‘A’ and ‘R’ functional groups respectively, generates hyperbranched polymer with peripheral alkyl bromide functional groups as shown in Figure 2. The peripheral alkylbromides has been quantitatively transformed to quaternary ammonium or pyridinium salts using trimethyl amine or pyridine respectively. Thus by the post polymerization modification, we have transformed a hydrophobic hyperbranched polymer to a water soluble cationic hyperbranched polymer by simple and efficient post-polymerization modification. In a slightly different objective we Another problem that I have addressed is the difficulty associated with the aforementioned copolymerization approach. In spite of the fact that stoichiometric amounts of ‘A-R’ type monomer was taken in ‘AB2 + A-R’ approach, the extent of peripheral functionalization i.e. the incorporation of ‘R’ group is relatively lower. Further the molecular weight of the hyperbranched polymer obtained is also not high. One of the reasons we adopted ‘AB2 + A-R’ approach is to provide a functional handle for the subsequent post-polymerization modification. We modified the ‘AB2’ type monomer with a functionalizable handle to circumvent the lower amount of incorporation of the ‘A-R’ type monomer in ‘AB2 + A-R’ approach. Of all the readily functionalizable handles, click chemistry found to be a very useful tool for the post-polymerization modifications as the reactions conditions are mild, no side product, high selectivity, easy purification, etc. Another advantage of this reaction is that, we can incorporate any type of functional group starting from a single clickable parent hyperbranched polymer. In this particular project, I have Earlier design of the ‘AB2’ type monomer in our group, to prepare hyperbranched polymer via melt transetherification process, involved benzylic methoxy groups as ‘B’ in ‘AB2’ monomer leading to a hyperbranched polymer with peripheral methoxy groups. Transetherification under melt-conditions is an equilibrium reaction which was driven towards the hyperbranched polymer by continuous removal of methanol from the system as a volatile alcohol. In the new design of ‘AB2’ monomer; we have used benzylic allyloxy groups as ‘B’ in ‘AB2’ monomer, where in polymerization is driven by the continuous removal of allyl alcohol (instead of methanol as in the previous case), generates hyperbranched polymer with peripheral allyloxy group containing hyperbranched polymer. The allyloxy groups can be subsequently functionalized with a variety of thiol, we prepared a hydrocarbon-soluble octadecyl-derivative, amphiphilic systems using 2-mercaptoethanol and chiral amino acid (N-benzoyl cystine) hyperbranched structures by using thiol-ene click reactions (Figure 3). Polymers prepared from the parent hyperbranched polymer have significantly different physical properties like glass transition temperature (Tg), melting point (Tm) etc; thus considering the versatility of functionalization, parent polymer could be envisioned as a clickable hyperscaffold. More interestingly by functionalizing cystine derivative, we have demonstrated the possibility of biconjugation of the hyperbranched polymer. In summary, the limitations of ‘AB2+A-R’ copolymerization approach (low molecular weight Molecular weight and molecular weight distribution are very important parameters that influence the physical property and thus the application of the polymeric materials. As predicted by Flory, hyperbranched polymers are inherently polydisperse in nature and it tends to infinity when the percent of conversion is very high. Experimentally observed value of polydispersity is also significantly higher compared to their linear analogues. Control of the molecular weight and polydispersity of hyperbranched polymer by using a suitable amount of reactive multifunctional core has been demonstrated in this project. We have substantiated by using very little amount of ‘B3’ core along with ‘AB2’ monomer; wherein ‘B’ in ‘B3’ are more reactive than ‘B’ in ‘AB2’ monomer, regulate the molecular weight and polydispersity of the resulting hyperbranched polymer. As the ratio of core to monomer increases the molecular weight and polydispersity reduces in nearly linear fashion. In a slightly different objective, the core and periphery are functionalized with two different fluorophore by using orthogonal click reactions and demonstrated the possibility of energy transfer from periphery to the core of the hyperbranched polymer. In this section of my thesis, the self-assembly behavior of a periodically grafted amphiphilic copolymer has been studied. Polymer was synthesized via melt transesterification approach where hexaethylene glycol monomethyl ether (HEG) containing diester monomers are reacted with alkylyne diol monomers with varying carbon spacer (C12 and Another interesting problem, I approached is to functionalize the interior part of the hyperbranched polymer. In the case of dendrimer, as it is a step-wise synthesis, internal functionalization could be accomplished with the order of monomer addition i.e. by putting the internal functional group containing monomer first followed by other monomer not having those functional groups, whereas it is a bit challenging task for hyperbranched polymers especially when dealing with polycondensation of AB2 monomers, as it is a single step polymerization process. For a hyperbranched polymer in the polycondensation of ‘AB2’ monomer, the internal functional group should reside in between of the ‘A’ and ‘B’ functional group wherein the internal functional groups are silent during the process of polymerization. In order to do so, we have designed and synthesized a new AB2 monomer (a in Figure: 4). Here decanol is the volatile condensate that was removed during the transetherification reactions leading to a hyperbranched polymer having allyl group as the internal functional group and decyloxy as the peripheral functional group (b in Figure: 4). As a post-polymerization modification, the interior allyl groups were modified by thiol-ene click reaction with variety of thiol derivatives. In one example, the inherent hydrophobic nature of the parent hyperbranched polymer which is enhanced by the decyl chain at the molecular periphery, is converted to a alkaline water soluble hyperbranched polymer by the click reaction with mercapto succinic acid (d in Figure: 4) or mercapto propionic acid (c in Figure: 4) to the internal allyl groups, generating a novel amphiphilic hypersystem. This kind of amphiphilic systems are very interesting to study for their self-assembly behavior, in this particular case, the modified hyperbranched polymer adopts as a large spherical aggregates in alkaline water evidenced by FESEM (Figure: 4) and AFM images. Further investigation is being carried out to understand the exact nature of these aggregates. As the hyperbranched polymer contained ‘-S-‘ group in the interior, we utilized this as the scaffold for scavenging heavy metal ions like Hg2+ from aqueous solutions to the chloroform solution containing polymer. This hyperbranched polymer could trap Hg2+ ions even when present in ppm level of contamination.

L'objectif principal de ce travail de thèse est la synthèse et l'étude des propriétés en solution de nouveaux copolymères amphiphiles di- et triblocks à gradient de styrène et d'acide acrylique qui sont capables d'association réversible en milieu aqueux. Nous avons étudié la cinétique et le mécanisme de la polymérisation radicalaire contrôlée par l’intermédiaire d’un nitroxyde (NMP), afin de déterminer les caractéristiques quantitatives des réactions de terminaison réversible lors de ce processus. Puis la NMP a été utilisée pour la synthèse de deux architectures différentes de copolymère à gradient: copolymères di- et triblocs. L'auto-assemblage des copolymères à gradient dans l'eau a été étudiée par DLS, SANS et TEM. Les changements réversibles du nombre d'agrégation au cours des cycles de pH ont été observés. De plus, nous avons étudié l'effet du pH et de la force ionique sur les propriétés rhéologiques en solution de copolymères triblocs à gradient. Nous nous sommes également intéressés à synthétiser des brosses de polymère sur surface d'or et étudié leur propriétés pH et électro-sensibles en milieu aqueux. / The main goal of our work was the synthesis and the study of solution properties of novel amphiphilic di- and triblock-gradient copolymers based on styrene and acrylic acid which are capable of reversible association in aqueous solution. We studied the kinetics and the mechanism of nitroxide-mediated radical polymerization (NMP) in order to determine the quantitative characteristics of the reversible termination reaction in this process. Then NMP was employed to the synthesis of two different block-gradient copolymer architectures: di- and triblock-gradient copolymers. The self-assembly of the block-gradient copolymers in water was studied by DLS, SANS and TEM. The reversible changes of aggregation numbers in cycles of pH were observed. We also investigated the effect of pH and ionic strength on rheological properties of triblock-gradient copolymer solution. Then, we synthesized polymer brushes on the gold-coated surface and studied their pH- and electro-responsive properties in aqueous media.

L’objectif de cette thèse est d’étudier la synthèse et les propriétés d’auto-assemblage en milieu aqueux de copolymères « intelligents » capables de former des agrégats supramoléculaires en réponse à deux stimuli : la température du milieu et la présence de dioxyde de carbone (CO2). Pour cela, une gamme de copolymères diblocs amphiphiles composés d’un bloc hydrophile d’acrylate de polyethylèneglycol méthyléther) (PEGA) et d’un bloc stimulable contenant une distribution statistique d’unités PEGA et acrylate de diéthlèneglycol éthyléther (DEGA) (thermosensibles) et acrylate de diéthylaminoéthyle DEAEA (CO2-sensible), a été préparée par polymérisation radicalaire contrôlée par les nitroxydes (NMP). Dans un second temps, il a été mis en évidence que la température ainsi que la présence de CO2 dans la solution influencent le comportement auto-associatif des copolymères dans l’eau. Par la suite, le bloc hydrophile a été remplacé par une séquence de dextrane, ce qui a permis de préparer de nouveaux copolymères diblocs fonctionnels, stimulables par la température et le CO2. Dans ce cas, deux techniques de polymérisation radicalaire contrôlée (NMP et ATRP) ont été testées afin d’obtenir les copolymères possédant l’architecture la mieux définie possible. / This project aims to investigate the synthesis and properties of dual stimuli-responsive block copolymers able to self-assemble into supramolecular aggregates in response to two stimuli: the temperature and the presence of carbon dioxide in the aqueous solution. Therefore, a range of amphiphilic diblock copolymers composed of a hydrophilic block of polyethylene glycol methylether acrylate (PEGA) and a statistical block of PEGA, diethylene glycol ethyl ether acrylate (DEGA) and diethylaminoethyl acrylate (DEAEA) was prepared via nitroxide-mediated polymerization (NMP) and the level of control of each synthesis was studied. We evidenced that temperature and CO2 play a different role in the self-assembly of such block copolymers. Finally, the introduction of dextrane as hydrophilic block coming from renewable resources allows for the preparation of novel “smart” amphiphilic diblock copolymers. In order to synthesize these block copolymers with well-defined structure, both NMP and atom transfer radical polymerization (ATRP) were investigated in parallel.

Dans le domaine des polymères, l'auto-organisation de la matière a été largement étudiée dans les dernières années et beaucoup de progrès dans le domaine des films ordonnés, générés par l'auto-assemblage de copolymères à blocs, ont été réalisés. Ce progrès est motivé par le fait que les films auto-assemblés possèdent des applications en biologie, photonique, adhésion. Le sujet initial de thèse est la fabrication des films structurés en nid d’abeilles formés par un bloc de copolymère contenant une partie hydrophobe ( à peu près 90%) et une partie hydrophile (10%) qui peuvent s’auto-organiser en nid d’abeilles. Les films de polymères préparés seront ultérieurement à la base d’une étude de complexation avec des métaux. Ceci sert à décontaminer les eaux usées des métaux ou pesticides. Durant ces années de thèse, une méthodologie d’analyse de surface est détaillée pour comprendre la topographie de ces films ainsi que la chimie de surface de ces derniers. Pour cette raison, divers techniques d’analyses sont utilisées pour décrire vigoureusement la surface de ces films afin d’optimiser ces films pour complexer les contaminants à origine industrielle.Une des techniques d’analyse de surface, i.e. TOF-SIMS (Time Of Flight-Secondary Ion Mass Spectroscopy), a prouvé être un outil efficace pour caractériser chimiquement la composition élémentaire et moléculaire de l’extrême surface et en profondeur. Cette technique était la technique de base de ces études. Elle la permis de décrire les empreintes spectrales ainsi que la distribution en surface et en profondeur de chaque polymère dans les films élaborés en nid d’abeilles. / Since its introduction in 1994, the preparation of ordered porous polymer films by the breath figure “BF” method has received a considerable interest. Self-organized porous polymer films, with pores ordered into a hexagonal pattern, can be elaborated by a fast solvent evaporation method under a humid atmosphere, also called “Breath Figure” approach. The honeycomb films have found a panel of perspective applications ranging from materials with optical properties, biomaterial sensors, and scaffold for tissue engineering or highly hydrophobic surfaces. The main objective of this PhD thesis project is the fabrication of sensitive hierarchically self-organized bio inspired films based on organic compound trapping block copolymers. It is worth noting that one of the advantages of using block copolymer structure is that the first block confers the hydrophobic character, required for the elaboration and stability of HC structure, and the second block could provide an additional functionality such as hydrophilicity, stimuli-responsive character or trapping of targeted molecules (especially metals).During this thesis, a methodology of surface analysis is performed in order to understand the topography of these films as well as its surface chemistry. For this reason, various analytical techniques are used to describe the surface of these films vigorously in order to optimize these films to complex industrial contaminants.One of the techniques of surface analysis, i.e. TOF-SIMS (Time of Flight-Secondary Ion Mass Spectroscopy), has proved to be an effective tool for chemical characterization of the surface and in depth. This technique was the basic technique of our studies. It allowed the description of spectral finger prints as well as the distribution on the surface and in depth of each polymer in the structured films.

Block copolymers are commercially significant and fundamentally interesting class of polymeric materials. The ability to undergo interfacial thermodynamics-controlled microphase separation from a completely disordered state in the melt to a specifically defined ordered structure through self-organization makes the block copolymers based materials unique. Block copolymer are strongly replacing many of the commercially available polymers due to their unique microstructure and properties. The most practical interests of block copolymers lie in the area of thermoplastic elastomers (TPEs). The objective of the present thesis work is to developing novel roots for enhancing the physical and mechanical properties in block copolymer and multigraft copolymers. Initially the properties are tailored by controlling chemical architecture at synthesis level and by selective blending at production level. This gives an easy access for improvement of the material properties and this is one of my major tasks in the present research modules. Further the block copolymer based TPEs are cross-linked in presence of electron beam (EB) radiation for developing materials with superior properties. The electron beam radiation has the ability to alter material parameters at molecular level for enhancing the macroscopic properties. The desirable physical and chemical properties can be easily attained by varying the radiation beam parameters. In addition to that, controlling the material at nanometer scale is one of the greatest challenges for current nanocomposite research. In elastomeric materials it is very prominent to fill the rubber matrix with nano particles from carbon or silica by melt mixing technique for enhancing the material properties. Other than conventional melt mixing technique, sol–gel processing is also a versatile technique, which making it possible to produce a wide variety of materials and to provide existing materials with novel properties. A combination of in situ sol-gel reaction with electron beam cross-linking in TPEs from triblock copolymer has been demonstrated for the first time as one of the novel nanocomposite system in this work. The main advantage of this system lies in controlling the material behaviour by finely tuning the size of silica nano particle generated inside TPE during in situ sol-gel reaction. Finally, the various roots employed for enhancing the material behaviour in block copolymers in the above research module were secussfully employed on super elastic multigraft copolymers for improving their strength withour sacrificing the super elastic nature.