Due to brittleness of polystyrene, PS, its usage area is restricted. To solve this problem and expand the usage area of PS, it can be blended and impact modified with an elastomeric material. In this study, the decrease in the modulus and tensile strength imparted by impact modification was overcome by reinforcing this mixture by incorporating organoclays and producing nanocomposites. This study consists of two parts. In the first part of this study three different types of aliphatic elastomeric materials and three different types of organoclays were used and their effects on the morphology, mechanical, thermal, and rheological properties of PS were investigated. Lotader AX8900, Lotader AX8840 and Lotader 2210 were chosen as the aliphatic elastomeric compatibilizers / and Cloisite

The synthesis of ion-exchange resin which can be used in various separation and chemical purposes, such as diffusion dialysis, electro dialysis, electrolysis and fuel cells has of considerable interest. For all these applications, the interactions of the ionic groups and the resulted morphologies are critical for establishing the unique properties. Considerable researches have been continued to understand the microstructure of these materials. The aim of this study is to synthesize polypropylene (PP) based ion exchange resins and to investigate their ion-exchange properties. In the first part of this study polypropylene was functionalized by grafting maleic anhydride onto the polypropylene and the product was characterized by ATR. The effect of maleic anhydride introduced to the grafting medium and the effect of the radical initiator on the maleic anhydride content of the MA-g-PP samples were investigated. In the second part, neutralization of the MA-g-PP samples with Na+, K+, Mg2+ and Ca2+ ions and peroxide cross-linking of neutralized MA-g-PP samples were performed. Characterization of the neutralized MA-g-PP samples were performed by ATR and SEM-EDX. In the last part of the study, ion exchange properties of MA-g-PP resins towards Cu2+, Co2+, Cd2+, Pb2+ and Fe3+ ions at different pHs were investigated by batch equilibrium method. Rate of metal uptake, concentration effect on the metal uptake and regeneration of the MA-g-PP samples were also examined.

Poly (co iso-butyl vinyl ether-alt-maleic anhydride), an alternating copolymer, was synthesised. For this class of copolymers the formation of an electron-donor complex is invoked to explain their microstructure in which the two comonomers strictly alternate. Due to its polarity, this copolymer constitutes a potential additive for imparting hydrophilic properties to a hydrophobic matrix. In order to obtain narrow molecular weight polymers and study the relation between the molecular weight of this additive and its ability to migrate to the host polymer surface, chain transfer agents were introduced in the system and also the Reversible Addition-Fragmentation chain Transfer (RAFT) process was employed. Free radical polymerisation was first carried out to allow for a comparison with the RAFT process and kinetics of copolymerisation was studied by NIR-FTIR and 1H NMR spectroscopy in order to analyse the rate of reaction of each comonomer. Dibenzyl trithiobenzoate, 3-benzyl sulfanyl thiocarbonyl sulfanyl-propionic acid and dibenzyl trithiobenzoate were used as RAFT agents. Results demonstrate that only benzyl dithiobenzoate is able to control the molecular weight of this copolymer and decrease its polydispersity index; possible reasons laying behind this result are discussed. It was also found that, in particular in the presence of benzyl dithiobenzoate, poly(iso-butyl vinyl ether) forms. This is an unusual phenomenon considering that the free radical polymerisation affords alternating copolymers and that iso-butyl vinyl ether is a monomer that polymerises through the cationic process. Experiments were carried out in various solvents in an attempt to counteract this side reaction, but no appreciable correlation between the properties of the solvents and the formation of homopolymer were found. Various hypothesis are considered, however it is likely that, in the conditions adopted, the presence of the RAFT agents alters the equilibrium constant of complex formation favouring the synthesis of the homopolymer. In addition to this side???reaction also inhibition of the copolymerisation reaction was at times encountered and an investigation into this phenomenon was also conducted.

Polipropileno (PP) é um termoplástico com ótimo balanço de propriedades, baixo custo e largo espectro de aplicações. Seu uso como material de engenharia é limitado pelos seus valores relativamente baixos de propriedades mecânicas. A adição de reforço ao PP melhora suas propriedades termomecânicas, tornando-o adequado para fabricação de peças de engenharia como composto termoplástico. Fibra de vidro (FV) é o reforço mais empregado em compostos de PP devido a maior resistência mecânica específica gerada no PP e por atuar como agente nucleante. Devido à diferença entre as naturezas das ligações secundárias, há pouca afinidade química entre PP-FV, sendo necessária a modificação interfacial através de agentes de acoplamento poliméricos (AA) para melhorar o desempenho termomecânico deste composto. Averiguou-se neste trabalho a influência de dois AA, um à base de PP e outro à base de EPDM, ambos graftizados com anidrido maleico (PAM e EAM, respectivamente), no comportamento térmico do composto PP∕FV. Os compostos PP30FV-AA foram preparados em extrusora dupla rosca ZSK 26, e posteriormente injetados em uma injetora Airburg para obtenção de corpos de prova utilizando teor fixo de 30% FV e teores de 0,5∕1,0∕2,0% AA. O PP e seus compostos foram caracterizados via microscopia óptica acoplada à placa Hot Stage, cristalização isotérmica e não isotérmica por calorimetria (DSC), resistência à deflexão térmica (HDT), morfologia da fratura (MEV) e comportamento viscoelástico (DMA) para analisar a influência do AA e da FV. Os resultados obtidos foram avaliados estatisticamente via metodologia ANOVA (Analysis of Variance). O efeito sinérgico FV-AA na cristalização isotérmica do PP foi dependente da combinação temperatura-natureza-teor de AA, sendo a temperatura o fator preponderante. A interação interfacial entre a matriz- reforço foi substancialmente favorecida pelo PAM. O uso de EAM retardou a cristalização do PP, enquanto que o PAM favoreceu este processo. Constatou-se que o AA teve pouca influência no tempo de meia-vida de cristalização nas menores isotermas e, para isotermas mais próximas à fusão do PP, o PAM apresentou menores valores deste parâmetro. Os valores de deflexão térmica foram semelhantes para todas as formulações contendo PAM, enquanto que a adição de EAM decresceu esta propriedade. Em temperaturas inferiores à transição vítrea (Tg) do PP, todos os compostos com AA apresentaram menor módulo elástico em relação ao composto puro; em temperaturas superiores à Tg, o PAM favoreceu aumentou esta propriedade na faixa de temperatura em que o composto usualmente é utilizado. / Polypropylene (PP) features by its properties balance, price and large array of applications. However, its use as engineering component is limited by relative low mechanical properties. PP reinforcement improves its thermomechanical properties, turning it into suitable to produce engineering components as a reinforced thermoplastic composite. Glass fiber (GF) is the most usual reinforce utilized in PP due to its great specific mechanical strength elastic modulus and nucleation capability. In reason of different secondary bonds between PP and GF, it is mandatory to modify the interface between these domains through polymeric coupling agents (CA) to improve thermomechanical performance. It was evaluated the influence of two CA based on PP and EPDM grafted with maleic anhydride (PAM and EAM) on thermal behavior of PP∕GF composite. PP30GF-CA composites were prepared in a twin screw extrusor ZSK 26 and injected in an injector Airburg with fixed GF content (30%) and different CA contents (0.5∕1.0∕2.0%). PP and PP composites were analyzed by optical microscopy with Hot Stage, isothermal and non-isothermal crystallization (DSC), as well as viscoelastic behavior. The results were statistically evaluated by ANOVA (Analysis of Variance) methodology. The synergic role between GF∕CA in PP crystallization was dependent on temperature-nature-CA content, mainly influenced by temperature. Interfacial adhesion was mainly favored by PAM. The results pointed a possible PP isotherm crystallization retardant by EAM, whereas PAM significantly favored this same process. CA presence in PP30GF composite did not influence crystallization half-life time values in lower isotherms, while in isotherms near PP melting temperature, PAM considerably decreased this parameter. Deflection thermal values were not affected by PAM, while EAM decreased this property in whole formulations. CA did not improved PP∕GF elastic modulus below PP glass transition (Tg), while in temperatures above Tg, PAM improved PP-GF this same parameter.

Polipropileno (PP) é um termoplástico com ótimo balanço de propriedades, baixo custo e largo espectro de aplicações. Seu uso como material de engenharia é limitado pelos seus valores relativamente baixos de propriedades mecânicas. A adição de reforço ao PP melhora suas propriedades termomecânicas, tornando-o adequado para fabricação de peças de engenharia como composto termoplástico. Fibra de vidro (FV) é o reforço mais empregado em compostos de PP devido a maior resistência mecânica específica gerada no PP e por atuar como agente nucleante. Devido à diferença entre as naturezas das ligações secundárias, há pouca afinidade química entre PP-FV, sendo necessária a modificação interfacial através de agentes de acoplamento poliméricos (AA) para melhorar o desempenho termomecânico deste composto. Averiguou-se neste trabalho a influência de dois AA, um à base de PP e outro à base de EPDM, ambos graftizados com anidrido maleico (PAM e EAM, respectivamente), no comportamento térmico do composto PP∕FV. Os compostos PP30FV-AA foram preparados em extrusora dupla rosca ZSK 26, e posteriormente injetados em uma injetora Airburg para obtenção de corpos de prova utilizando teor fixo de 30% FV e teores de 0,5∕1,0∕2,0% AA. O PP e seus compostos foram caracterizados via microscopia óptica acoplada à placa Hot Stage, cristalização isotérmica e não isotérmica por calorimetria (DSC), resistência à deflexão térmica (HDT), morfologia da fratura (MEV) e comportamento viscoelástico (DMA) para analisar a influência do AA e da FV. Os resultados obtidos foram avaliados estatisticamente via metodologia ANOVA (Analysis of Variance). O efeito sinérgico FV-AA na cristalização isotérmica do PP foi dependente da combinação temperatura-natureza-teor de AA, sendo a temperatura o fator preponderante. A interação interfacial entre a matriz- reforço foi substancialmente favorecida pelo PAM. O uso de EAM retardou a cristalização do PP, enquanto que o PAM favoreceu este processo. Constatou-se que o AA teve pouca influência no tempo de meia-vida de cristalização nas menores isotermas e, para isotermas mais próximas à fusão do PP, o PAM apresentou menores valores deste parâmetro. Os valores de deflexão térmica foram semelhantes para todas as formulações contendo PAM, enquanto que a adição de EAM decresceu esta propriedade. Em temperaturas inferiores à transição vítrea (Tg) do PP, todos os compostos com AA apresentaram menor módulo elástico em relação ao composto puro; em temperaturas superiores à Tg, o PAM favoreceu aumentou esta propriedade na faixa de temperatura em que o composto usualmente é utilizado. / Polypropylene (PP) features by its properties balance, price and large array of applications. However, its use as engineering component is limited by relative low mechanical properties. PP reinforcement improves its thermomechanical properties, turning it into suitable to produce engineering components as a reinforced thermoplastic composite. Glass fiber (GF) is the most usual reinforce utilized in PP due to its great specific mechanical strength elastic modulus and nucleation capability. In reason of different secondary bonds between PP and GF, it is mandatory to modify the interface between these domains through polymeric coupling agents (CA) to improve thermomechanical performance. It was evaluated the influence of two CA based on PP and EPDM grafted with maleic anhydride (PAM and EAM) on thermal behavior of PP∕GF composite. PP30GF-CA composites were prepared in a twin screw extrusor ZSK 26 and injected in an injector Airburg with fixed GF content (30%) and different CA contents (0.5∕1.0∕2.0%). PP and PP composites were analyzed by optical microscopy with Hot Stage, isothermal and non-isothermal crystallization (DSC), as well as viscoelastic behavior. The results were statistically evaluated by ANOVA (Analysis of Variance) methodology. The synergic role between GF∕CA in PP crystallization was dependent on temperature-nature-CA content, mainly influenced by temperature. Interfacial adhesion was mainly favored by PAM. The results pointed a possible PP isotherm crystallization retardant by EAM, whereas PAM significantly favored this same process. CA presence in PP30GF composite did not influence crystallization half-life time values in lower isotherms, while in isotherms near PP melting temperature, PAM considerably decreased this parameter. Deflection thermal values were not affected by PAM, while EAM decreased this property in whole formulations. CA did not improved PP∕GF elastic modulus below PP glass transition (Tg), while in temperatures above Tg, PAM improved PP-GF this same parameter.

Orientador: Carlos Roque Duarte Correia / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-17T04:40:41Z (GMT). No. of bitstreams: 1 Miranda_KarenFabianeCanto_D.pdf: 2096574 bytes, checksum: b7fd48d07ff428a29ed0b7b0b0c1ad8c (MD5) Previous issue date: 2010 / Resumo: O primeiro capítulo deste trabalho concentra-se no estudo metodológico da reação de Heck com anidrido maleico empregando diversos sais de arenodiazônio. A reação foi investigada em diversas condições e, num primeiro momento, foi possível, utilizando acetato de paládio como catalisador, preparar uma série de anidridos maleicos mono e diarilados através da reação com sais de diazônio contendo grupos doadores de elétrons. Também investigou-se a reação empregando sais de diazônio contendo grupos retiradores de elétrons, entretanto, com o sistema catalítico utilizado inicialmente, não foi possível obter os correspondentes anidridos maleicos substituídos. A utilização do catalisador POPd solucionou o problema do emprego de sais de diazônio contendo grupos retiradores de elétrons. Desse modo foi possível preparar uma série de anidridos maleicos mono e diarilados, com diferentes demandas eletrônicas e padrões de substituição, em rendimentos satisfatórios. Além disso, foi possível preparar também anidridos maleicos dissubstituídos simétricos e não simétricos. Vários dos anidridos maleicos preparados apresentaram fluorescência. O segundo capítulo mostra a aplicabilidade da metodologia desenvolvida. É apresentada a síntese do alcalóide de origem marinha Policitrina A através de uma rota sintética curta, que tem como etapas chaves duas reações de Heck consecutivas com anidrido maleico empregando sal de diazônio. Neste capítulo também são mostrados os esforços visando à síntese total do alcalóide Policitrina B e a síntese formal do mesmo / Abstract: Chapter one of this work deals with methodological studies of the Heck reaction with maleic anhydride using several arenediazonium salts. Several reaction conditions were investigated and at first, it was possible by the use of palladium acetate as catalyst, to prepare a series of mono and diarylated maleic anhydrides through reaction with diazonium salts bearing electron donating groups. The reactions using diazonium salts bearing electron withdrawing groups were also investigated although, with the previous catalytic system used, the correspondent substituted maleic anhydrides weren¿t obtained. The use of POPd catalyst solved the problematic use of diazonium salts bearing electron withdrawing groups. In this way, it was possible to prepare a series of mono and diarylated maleic anhydrides, with different electron demanding conditions and substitution patterns, with satisfactory yields. Besides this, it was possible to prepare symmetric and non-symmetric bi-substituted maleic anhydrides too. Several of this maleic anhydrides prepared displayed fluorescence. Chapter two presents applications of the methodology developed in chapter one. The synthesis of marine alkaloid Polycitrin A is presented through a short synthetic route which has as key steps two consecutive Heck reactions with maleic anhydride using diazonium salt. Efforts towards total synthesis of alkaloid Polycitrin B as well as its formal synthesis are also shown in this chapter / Doutorado / Quimica Organica / Doutor em Ciências

La thèse porte sur l’étude de la morphologie et des différentes propriétés thermiques, mécaniques et barrières à la vapeur d’eau des nanobiocomposites à base de poly acide lactique (pla). La première partie est consacrée au greffage de l’anhydride maléique (am) sur le poly acide lactique plagma et à la mise en oeuvre de nanobiocomposites pla/cloisites, plagma/cloisites et pla/plagma/cloisites en utilisant deux cloisites® différentes (c20a et c30b), préparés par voie fondue. Au travers des différentes techniques utilisées, les résultats révèlent que les nanobiocomposites pla/cloisites élaborés se caractérisent par une morphologie mixte intercalée-exfoliée. L’ensemble des échantillons élaborés indiquent une meilleure dispersion de la cloisite apolaire c20a en présence de l’anhydride maléique et la réagrégation de la cloisite polaire c30b et par conséquent, l’amélioration à la fois des propriétés mécaniques et barrières à la vapeur d’eau des nanobiocomposites à base de la c20a. La seconde partie traite l’influence des groupements fonctionnels d’oxyde de graphène synthetisé au laboratoire et de graphène fonctionnalisé époxy commercialisé et fournit par nanovia (france) sur la dispersion des nanofeuillets de graphène au sein de la matrice pla, en présence ou en absence du compatibilisant plagma. L’étude révèle que la présence du compatibilisant améliore la dispersion de deux nanocharges étudiées. Le maximum des performances rhéologiques indiquant la meilleure dispersion de la nanocharge est enregistré pour une faible quantité d’oxyde de graphène possédant plus de groupements fonctionnels contenant l’atome d’oxygène. Les propriétés thermiques et barrières ont été considérablement améliorées avec l’incorporation des deux nanocharges et en présence de l’agent compatibilisant plagma. L’étude montre aussi que les propriétés mécaniques en traction des nanobiocomposites à base de graphène fonctionnalisé époxy (gfe) ont été améliorées en présence du plagma. / The thesis focuses on the study of the morphology and thermal, mechanical and barrier properties of the nanobiocomposites based on poly lactic acid (pla). The first part is devoted to the grafting of maleic anhydride (ma) on the poly lactic acid plagma and the elaboration of the nanobiocomposites pla/cloisites, plagma/cloisites and pla/plagma/cloisitres using two different cloisites (c20a and c30b), prepared by melt intercalation and the characterization of the main properties. The results indicate that the pla/cloisites nanobiocomposites exhibit a mixed intercalated-exfoliated morphology. All the prepared samples showed an improvement in both thermal, mechanical and barrier properties in the presence of the nanofiller. All prepared samples show better dispersion of apolar cloisite (c20a) in the presence of maleic anhydride and reaggregation of the polar cloisite (c30b) and therefore, the improvement of both the mechanical and barrier properties of the nanobiocomposites based on c20a. The second section discusses the effect of the functional groups of graphene oxide synthetized in the laboratory and the graphene fonctionnalized epoxy marketed and supplied by nanovia (france) on the dispersion of the graphene nanofillers in the pla matrix. The study reveals that the presence of compatibilizer improves the dispersion of two studied nanofillers. Maximum rheological performance indicating better dispersion of the nanofiller is registered for a small amount of graphene oxide (og) with more functional groups containing oxygen atom. The thermal and barriers properties have been considerably improved with the incorporation of two nanofillers and in the presence of plagma compatibilizer. The study also shows that the tensile properties of the pla containing graphene functionalized epoxy (gfe) were improved in the presence of plagma.

Condensation of 2,3-dichloromaleic anhydride and o-phenylenediamine in refluxing toluene affords the three compounds 2,3-dichloro-N-o-C6H4(NH2)maleimide (1), N,N¢-o-C6H4-bis(2,3-dichloromaleimide) (2), and 2,3-dichloropyrrolo[1,2-a]benzimidazol-1-one (3), with compound 1 as the major product. Repeating the same reaction in the presence of added PTSA furnishes compound 3 as the major product. Treatment of 3 with methylthiol in the presence of pyridine affords monosulfide compounds 2-chloro-3-methylthiopyrrolo[1,2-a]benzimidazol-1-one (4) and and the disulfide derivatives 2,3-di(methylthio)pyrrolo[1,2-a]benzimidazol-1-one (5). The substitution of the first chlorine group in compound 3 occurs regioselectively at C-3 to produce compound 4, followed by replacement of the remaining chlorine group to furnish the disulfide compounds 5. The new compounds 1-5 have been isolated by column chromatography and characterized by IR, NMR, XRD, CV and etc.

The diploma thesis deals with the heterogeneous technique of preparation of grafted polypropylene g maleic anhydride (PP-g-MAH). The knowledge of the course of the reaction and its impact on the PP grafting process are summarized in the theoretical part. The preparation of the grafted PP was carried out in a fluidized polymerization reactor at 115 °C, speed of mixing 210 rpm, reaction time 60 min and pressure 6 bar. The amount of grafted MAH was monitored by using a MAH concentration 3 and 5 wt% and an initiator concentration 0.25; 0.5; 1; and 1.5 wt%. Modification efficiency was compared by using 3 types of PP with different particle morphology and specific surface area. By creating the theoretical model, the maximum surface concentration of MAH was calculated and compared with experimental data. Characterization of PP materials was performed by Electron Scanning Microscopy (SEM), Differential Scanning Calorimetry (DSC) and particle surface analysis by BET. Quantitative analysis of grafted MAH was determined by FTIR spectroscopy and acid-base titration.

Diplomová práce se zabývá roubováním maleinanhydridu a anhydridu kyseliny itakonové na kyselinu poly(mléčnou) (PLA). U modifikované kyseliny poly(mléčné) byla sledována závislost konverze monomerů na různých molárních poměrech monomer/iniciátor při teplotách 180°C a 200°C. Množství naroubovaného monomeru bylo stanovováno acidobazickou titrací a pomocí FT-IR spektroskopií. Vliv stupně naroubování na krystalinitu modifikované PLA byl zjišťován pomocí diferenční kompenzační kalorimetrie, DSC. Degradace PLA byla orientačně pozorována pomocí indexu toku taveniny, MFI.