Les travaux présentés dans cette thèse portent sur le contrôle de la polymérisation radicalaire de l'éthylène à basse pression (200 bar) et basse température (70 °C) et sur la synthèse de copolymères à blocs contenant au moins un segment de polyéthylène. Quatre techniques de polymérisation, couramment utilisées en ingénierie macromoléculaire, ont été étudiées : NMP, CMRP, RAFT/MADIX et ESCP. Nos études sur le nitroxyde SG1 (NMP) et le bis(acétylacétonate) de cobalt (CMRP) ont montré que ces composés sont inefficaces pour contrôler la polymérisation de l'éthylène. Un comportement inattendu du bis(acétylacétonate) de cobalt a cependant été mis en évidence. Il semblerait que ces complexes de cobalt favorisent les réactions de couplage entre les radicaux propagateurs. En revanche, la première polymérisation radicalaire contrôlée de l'éthylène a été atteinte grâce à l'utilisation de xanthates (RAFT/MADIX). Les polyéthylènes synthétisés possèdent des masses molaires qui augmentent linéairement avec la conversion et des dispersités faibles. Le caractère pseudo-vivant de la réaction a été démontré par la synthèse de copolymères à blocs poly(acétate de vinyle)-b-polyéthylène. L'utilisation de nitrones (ESCP) a également permis l'introduction d'une fonction réactive au centre des chaînes de polyéthylène et la synthèse de copolymères triblocs de type ABA, où les blocs latéraux A sont en polystyrène ou polyacrylate et le bloc central B est en Polyéthylène / The work presented in this thesis displays the controlled radical polymerization of ethylene at low temperature (70 °C) and low pressure (200 bar) and the synthesis of block copolymers featuring polyethylene segments. Four polymerization techniques, commonly used in macromolecular engineering, were studied: NMP, CMRP, RAFT/MADIX and ESCP. Our investigation of the use of SG1 nitroxide (NMP) and cobalt (II) acetylacetonate (CMRP) as controlling agents demonstrated their inability to control the polymerization of ethylene. Nonetheless, an unexpected reaction with cobalt (II) acetylacetonate was observed. The coupling reaction between propagating radicals appeared to be favored by the presence of this compound. On the other hand, the first controlled polymerization of ethylene was successfully achieved by using xanthate (RAFT/MADIX). A linear increase of molecular weight with conversion and low polydispersities were observed for the produced polyethylenes. The reaction was demonstrated to be a pseudo-living polymerization by the synthesis of block copolymers poly(vinyl acetate)-b-polyethylene. In addition, midchain-functionalized polyethylenes and ABA type block copolymers, with polystyrene or polyacrylate as the A block and polyethylene as the B block, were also prepared using nitrone based polymerization technique (ESCP)

This work addresses the distribution of N-methylolacrylamide (NMA) units in crosslinking poly(vinyl acetate) (PVAc) adhesives. In this case, distribution refers to the three potential locations of polymerized NMA units in a latex: the water-phase, the surface of polymer particles, and the core of the polymer particles. The objective is to identify the distribution of NMA in three latices and to determine whether NMA distribution correlates with durability related performance. NMA distribution was studied via a series of variable temperature solution NMR experiments, while the durability-related performance was studied via mode I fracture mechanics tests. Studying the distribution of NMA required the use of isotopically labeled NMA. Both 15N-NMA and 13C, 15N-NMA were synthesized. Three NMA/vinyl acetate (VAc) latices were prepared. The NMA feed strategy was varied during each of the three emulsion copolymerizations. Latex characterization methods including differential scanning calorimetry (DSC), rheometry, particle size analysis, and scanning electron microscopy (SEM) were used to study the three latices. The solution NMR method to identify NMA distribution was performed on untreated latices and on washed latices. Washing techniques included membrane dialysis and centrifugation. Results revealed that the three latices had different NMA distributions, and that the distributions were related to the expected differences in microstructure. Latex 3 had ~ 80% core-NMA, while Latex 2 had ~ 80% surface-NMA. Latex 1 had a high proportion of surface-NMA (~60%), but also had the highest proportion of water-phase NMA (~ 20%). This high proportion of water-phase NMA could be responsible for the unique morphology Latex 1 exhibited in SEM studies. Mode I opening fracture mechanics studies were used to study adhesive performance. Specimens were analyzed after exposure to accelerated aging treatments. Latex 2 and Latex 3 exhibited very similar results, despite having very different NMA distributions. All three latices showed good durability related performance. In Latex 2 and Latex 3, the critical strain energy release rates (Gc) after accelerated aging treatments were statistically the same as the Gc of the control specimens. The most interesting finding was that the Latex 1 Gc values were significantly higher after accelerated aging. Latex 1 also had the highest proportion of water-phase NMA. Bondline images and SEM micrographs both indicated that the integrity of Latex 1 was least affected by the accelerated aging treatments. / Ph. D.

No description available.

To produce a greener adhesive is always an issue of concern to the commercial market and global environment. The environmental request for producing greener and bio-based adhesives leads to an increased awareness of replacing fossil-based components in adhesives with bio-based alternatives. Consequently, many researchers try to graft polymers from natural materials and some achievements have been made. In this work, an improved procedure to graft vinyl acetate (VAc) from chitosan (CS) is proposed and significant improvements were made regarding the increased Tg and water resistance. The achieved monomer conversion of VAc was ~97 %, and it was confirmed that chitosan-graft-poly(vinyl acetate) (CS-g-PVAc) could be used as a wood adhesive. The adhesive exhibited competitive properties to commercial PVAc wood adhesive. In the produced CS-g-PVAc, ~17 % of the fossil-based content of VAc could be replaced with bio-based chitosan, indicating an increased sustainability. At the same time there is no residual monomer during pressing, which avoid to pollute environment and hurt human. Compared to commercial PVAc, which has Tg at ~28 ℃, the Tg of CS-g-PVAc is ~42 ℃ At the same time, the water resistance of PVAc adhesive was successfully increased.

Ces travaux de thèse portent sur la polymérisation radicalaire contrôlée (PRC) des esters et amides de vinyle. L’une des possibilités de contrôle est le piégeage dynamique réversible des chaînes radicalaires croissantes (P•) par un agent de contrôle (T) formant une espèce dormante (P─T’). La concentration en radicaux dans le milieu peut alors diminuer dramatiquement de sorte que les réactions indésirables de terminaisons soient négligeables et que le contrôle de la masse molaire des polymères soit atteint avec un faible indice de dispersité. L’utilisation de complexes métalliques, pouvant s’oxider et former une liaison métal-carbone, comme agent de piégeage des radicaux est une manière de réaliser ce contrôle. La PRC est alors appelée Polymérisation Radicalaire Contrôlée par voie Organométallique (OMRP). A ce jour, plusieurs métaux de transitions ont été utilisés avec plus ou moins de succès en OMRP. Lors de cette étude, nous avons synthétisé des complexes de cuivre(I) et testé leurs performances pour l’OMRP de l’acétate de vinyle et de l’éthylène. Nous avons également utilisé des outils de chimie théorique pour mieux comprendre pourquoi le cobalt(II) acétylacétonate est, jusqu’à aujourd’hui, le meilleur agent de contrôle pour la polymérisation de l’acétate de vinyle et des amides de vinyle. Grâce à la théorie de la fonctionnelle de densité (DFT), nous avons mis en lumière le rôle crucial de la coordination sur le cobalt des groupements carbonyles des monomères étudiés. / This thesis focus on Controlled Radical Polymerization (CRP) of vinyl esters and vinyl amides. One of the possibilities to achieve this control is a dynamic reversible trapping of the growing radical chains (P•) by a controlling agent (T) to form a dormant species (P─T’). The radical concentration in the medium can be dramatically reduced so that the unwanted terminations are disfavored and polymers with controlled molecular weights and low dispersity can be obtained. A way to achieve this control is the use of metallic complexes, which can oxidize and form a metal-carbon bond, as trapping agent in the so-called Organometallic Mediated Radical Polymerization (OMRP). So far, different transition metals have been used with gretaer or smaller success. In this study, the synthesis of copper(I) complexes and their investigation for the vinyl acetate and ethylene polymerization under OMRP conditions were performed. We also used computational chemistry as a tool to better understand why the cobalt(II) acetylacetonate (Co(acac)2) has, so far, given the best results for either vinyl acetate or vinyl amides polymerization. Thanks to Density Functional Theory (DFT), the crucial role of the monomer carbonyl group coordination to cobalt was pointed out.

The objective of this research was to develop high performing polymer modified calcium sulfoaluminate (CSA) cement materials for use in applications requiring superior adhesion characteristics. Little information is available describing interactions of CSA cement containing minor phase tri-calcium aluminate (C3A) with commonly used admixtures. Given the scarcity of information, a basic approach for developing cementitious materials was followed. The basic approach consisted of four tasks: cement design, admixture design, polymer design and testing developed materials. The iterative, time consuming process is necessary for understanding the influence of specific constituent components on overall system behavior. Results from the cement design task suggest calcium sulfate type influences microstructural characteristics and strength development for materials based upon the experimental CSA cement. Results from the admixture design task suggest lithium carbonate and tartaric acid are effective accelerating and retarding admixtures for hydration reactions including reactants yeelimite, calcium sulfate and water. Results from the polymer design task suggest vinyl acetate / ethylene (VAE) dispersible polymer powders (DPP) are compatible with systems containing the experimental CSA cement and other commonly used admixtures. Additionally, results from the polymer design task highlight a method for specifying the ductile behavior of materials containing the experimental CSA cement as majority hydraulic binding agent. Finally, results from the testing of developed materials task suggests adhesion performance for materials containing the experimental CSA cement can be influenced by adjusting the ratio of polymer to hydraulic binding agent in material formulations. Polymer modified CSA cement mortars demonstrated bond strength resulting in substrate failure when cast over porous concrete substrates. Developed mortars demonstrated consistent bonding performance when applied to non-porous substrate materials, metal and glass. Select polymer modified mortars displayed adhesion bond performance such that the glass substrate materials fractured during pull off testing.

Neste trabalho foram estudados compósitos que apresentam como matriz polimérica uma blenda composta por polietileno de alta densidade (HDPE) e copolímero etileno acetato de vinila (EVA) e como nanocarga, silsesquioxano poliédrico oligomérico (POSS). Os compósitos foram processados em câmara de mistura fechada e caracterizados quanto às propriedades térmicas e morfológicas. Para a preparação dos compósitos foram variadas as concentrações dos componentes da blenda (0, 25, 50, 75 e 100%) e da nanocarga (0, 0,5, 1, 1,5, 2, 5 e 10%). Os resultados de processamento mostraram que o aumento da concentração de POSS na matriz polimérica provocou a agregação do mesmo na matriz polimérica. As análises de calorimetria diferencial de varredura e termogravimetria indicaram que o POSS não afetou as temperaturas de fusão, cristalização e degradação da matriz polimérica. Os resultados de raios X indicaram que a presença do EVA no compósito promoveu o aparecimento de domínios cristalinos em concentrações menores de POSS. A microscopia eletrônica de varredura indicou que as amostras com 1% de POSS apresentam distribuição homogênea na matriz polimérica. Por outro lado, ocorreu a formação de agregados nas amostras com 5% de POSS. Os valores de Tg obtidos por análise térmica dinâmico-mecânica indicaram que o POSS causou um efeito plastificante na fase HDPE e uma redução da mobilidade na fase EVA. Ocorreu um aumento nos valores de módulo de armazenamento com a incorporação de POSS na matriz polimérica. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-05-22T19:03:21Z No. of bitstreams: 1 Dissertacao Patricia Scapini.pdf: 2020883 bytes, checksum: 2c7249d3915135dd5f3cba151cf459db (MD5) / Made available in DSpace on 2014-05-22T19:03:21Z (GMT). No. of bitstreams: 1 Dissertacao Patricia Scapini.pdf: 2020883 bytes, checksum: 2c7249d3915135dd5f3cba151cf459db (MD5) / In this study composites with a polymeric matrix comprising a blend of high density polyethylene (HDPE) and the copolymer ethylene vinyl acetate (EVA), and with polyhedral oligomeric silsesquioxane (POSS) as the nanoclay, were processed and characterized. The composites were processed in a closed mixing chamber and characterized in terms of their thermal and morphological properties. For the preparation of the composites the concentrations of the blend components (0, 25, 50, 75 and 100%) and of the nanoclay (0, 0.5, 1, 1.5, 2, 5 and 10%) were varied. The results of the processing showed that an increase in the POSS concentration in the polymeric matrix caused the aggregation of the system. The differential scanning calorimetry and thermogravimetry analyses indicated that the POSS did not affect the melt, crystallization and degradation temperatures of the polymeric matrix. The X-ray results indicated that the presence of EVA in the composite led to the appearance of crystalline domains at lower POSS concentrations. Scanning electron microscopy indicated that the samples with 1% of POSS have a homogeneous distribution in the polymeric matrix. However, the formation of aggregates occurred in samples with 5% of POSS. The Tg values obtained from the thermo dynamic mechanical analysis indicated that the POSS had a plasticizing effect on the HDPE phase and caused a reduction in the mobility of the EVA phase. There was an increase in the storage modulus values with the incorporation of POSS into the polymeric matrix.

Neste trabalho foram estudados compósitos que apresentam como matriz polimérica uma blenda composta por polietileno de alta densidade (HDPE) e copolímero etileno acetato de vinila (EVA) e como nanocarga, silsesquioxano poliédrico oligomérico (POSS). Os compósitos foram processados em câmara de mistura fechada e caracterizados quanto às propriedades térmicas e morfológicas. Para a preparação dos compósitos foram variadas as concentrações dos componentes da blenda (0, 25, 50, 75 e 100%) e da nanocarga (0, 0,5, 1, 1,5, 2, 5 e 10%). Os resultados de processamento mostraram que o aumento da concentração de POSS na matriz polimérica provocou a agregação do mesmo na matriz polimérica. As análises de calorimetria diferencial de varredura e termogravimetria indicaram que o POSS não afetou as temperaturas de fusão, cristalização e degradação da matriz polimérica. Os resultados de raios X indicaram que a presença do EVA no compósito promoveu o aparecimento de domínios cristalinos em concentrações menores de POSS. A microscopia eletrônica de varredura indicou que as amostras com 1% de POSS apresentam distribuição homogênea na matriz polimérica. Por outro lado, ocorreu a formação de agregados nas amostras com 5% de POSS. Os valores de Tg obtidos por análise térmica dinâmico-mecânica indicaram que o POSS causou um efeito plastificante na fase HDPE e uma redução da mobilidade na fase EVA. Ocorreu um aumento nos valores de módulo de armazenamento com a incorporação de POSS na matriz polimérica. / In this study composites with a polymeric matrix comprising a blend of high density polyethylene (HDPE) and the copolymer ethylene vinyl acetate (EVA), and with polyhedral oligomeric silsesquioxane (POSS) as the nanoclay, were processed and characterized. The composites were processed in a closed mixing chamber and characterized in terms of their thermal and morphological properties. For the preparation of the composites the concentrations of the blend components (0, 25, 50, 75 and 100%) and of the nanoclay (0, 0.5, 1, 1.5, 2, 5 and 10%) were varied. The results of the processing showed that an increase in the POSS concentration in the polymeric matrix caused the aggregation of the system. The differential scanning calorimetry and thermogravimetry analyses indicated that the POSS did not affect the melt, crystallization and degradation temperatures of the polymeric matrix. The X-ray results indicated that the presence of EVA in the composite led to the appearance of crystalline domains at lower POSS concentrations. Scanning electron microscopy indicated that the samples with 1% of POSS have a homogeneous distribution in the polymeric matrix. However, the formation of aggregates occurred in samples with 5% of POSS. The Tg values obtained from the thermo dynamic mechanical analysis indicated that the POSS had a plasticizing effect on the HDPE phase and caused a reduction in the mobility of the EVA phase. There was an increase in the storage modulus values with the incorporation of POSS into the polymeric matrix.

Polyethylene (PE) resins being non-polar in nature and having a high degree of crystallinity have limited miscibility and compatibility when blended with polar polymers. The miscibility and compatibility of these blends are generally worsened when they are prepared by direct injection moulding without a precompounding process. Such situations are commonly encountered in particular by polymer converters when blending colour and/or additive concentrates, commonly known as masterbatches. Typically, masterbatches are mixtures containing high loading of pigments and/or additives predispersed in a suitable solid vehicle (commonly known as carrier) such as a polyethylene resin. These masterbatches are usually used for the colouration of a wide range of polymers and the carrier used must therefore be compatible with these matrix (host) polymers. The preliminary stage of this study involved the investigation of the properties of blends based on high density polyethylene (HDPE) and a range of engineering thermoplastics (ABS, PC, PBT, PA6), prepared by injection moulding. Five different types of compatibilisers namely, ethylene-vinyl acetate (EVA) copolymer, ethylene-methyl acrylate (EMA) copolymer, ethylene-glycidyl methacrylate (E-GMA) copolymer, ethylene-methyl acrylateglycidyl methacrylate (E-MA-GMA) terpolymer and maleic anhydride grafted HDPE (HDPE-g-MAH) copolymer were evaluated with respect to their efficiencies in compatibilising HDPE with the four engineering polymers. The pre-compounded HDPE/compatibiliser binary blends at 2 different blend ratios (1:1 and 3:1) were added at 15 wt% concentration to each engineering thermoplastics and test samples were produced directly by injection moulding. Results of mechanical testing and characterisation of the blends showed that glycidyl methacrylate compatibilisers, E-MA-GMA, in particular have the most universal compatibilising effectiveness for a range of engineering thermoplastics including ABS, PC, PBT, and PA6. Blends compatibilised with E-MA-GMA compatibiliser had the best notched impact performance irrespective of matrix polymer type. The presence of an acrylic ester (methyl acrylate) comonomer in E-MA-GMA resulted in increased polarity of the ii compatibiliser leading to improved miscibility with the polar matrix polymers demonstrated by fine blend morphologies, melting point depression and reduction in crystallinity of the HDPE dispersed phase. The second stage of this study involved the reactive modification of HDPE using a low molecular weight di-functional solid diglycidyl ether of bisphenol A (DGEBA) type epoxy resin compatibilised with HDPE-g-MAH in an attempt to improve its compatibility with ABS, PBT and PA6. The maleic anhydride moieties in HDPE-g-MAH served as reactive sites for anchoring the epoxy moieties while the HDPE backbone was miscible with the HDPE resin. An excessive amount of reactive groups resulted in the formation of crosslinked gels while the addition of EVA co-compatibiliser helped in the reduction of gel content and further improved the dispersion of the epoxy. The effectiveness of epoxy grafted HDPE (with and without EVA co-compatibiliser) in compatibilising ABS/HDPE, PBT/HDPE, and PA6/HDPE was investigated by injection moulding of 5 wt% functionalised HDPE with these matrix polymers into test bars for mechanical testing, and characterisation by differential scanning calorimtery (DSC) and optical microscopy. The reactively functionalised HDPE blends, improved the mechanical properties of ABS and PA6 blends especially with EVA as co-compatibiliser. However, the mechanical properties of PBT blends were unmodified by the functionalised HDPE which was believed to be due to end-capping of the PBT chain-ends by ungrafted epoxy resins.

Les gazoles, carburant automobile préféré des français, sont « additivés » afin de permettre leur utilisation en hiver. Les n-paraffines présentes dans ces gazoles cristallisent en effet à basse température. Ces cristaux peuvent alors entraîner le colmatage des filtres protecteurs situés en amont du moteur. Des polymères à base d'éthylène, notamment les copolymères éthylène-acétate de vinyle (EVA), sont utilisés pour abaisser la température à laquelle les problématiques de filtration adviennent. Un nouveau procédé de copolymérisation radicalaire d'éthylène et d'acétate de vinyle, à plus basse pression et à plus basse température, que le procédé industriel actuel, a été développé au cours de cette thèse. Une grande variété d'EVA a ainsi été obtenue. Ils présentent des caractéristiques structurelles et une efficacité, pour le traitement des gazoles, similaires aux EVA commerciaux. Ce procédé a, par ailleurs, permis la synthèse d'autres co- et terpolymères de l'éthylène variant par la nature des comonomères polaires utilisés ou par l'architecture. Des modèles de copolymères EVA ont été également synthétisés par métathèse. La grande diversité d'additifs polymères à disposition combinée à des techniques d'analyse thermique et de diffusion des rayons X mises en oeuvre au plus proche de l'application (en particulier dans le gazole), ont permis de mieux appréhender leur mode d'action sur la cristallisation des n-paraffines. Les spécificités structurelles, des polymères, conditionnant leur efficacité pour le traitement de la tenue à froid des gazoles ont également pu être établies / The additivation of diesel fuels allows operating engines at low temperatures without filter blocking and thus fulfilling legal requirements. Ethylene based copolymers such as ethylene-vinyl acetate copolymers, made by free radical polymerization at high pressure (above 2000 bars) and high temperature (above 200 °C) are frequently used as middle distillate cold flow improvers (MDFI). A new free radical copolymerization process of ethylene and vinyl acetate in organic solvent media has been developed. This process gives access to polymers close to commercial MDFI additives under tremendous less drastic conditions (under 250 bars of ethylene and 70 °C). Thanks to this process, a wide diversity (variation of the nature of the polar unit, of polymer architecture…) of ethylene based polymers was obtained. Moreover, EVA model copolymers have been synthesized by metathesis. Thanks to these numerous and diverse ethylene based polymers combined with thermal analysis and X-ray scattering studies a better understanding of the operating mode of these additives in a diesel fuel has been achieved. The structural characteristics of the polymers enabling their effectiveness as diesel fuel cold flow improvers have also been established