Die RAFT-Polymerisation ("Reversible Addition-Fragmentation Chain Transfer") ist eine radikalische Polymerisation, die auf dem Prinzip des degenerativen Kettentransfers basiert. Es können Polymere hergestellt werden, die eine niedrige Dispersität aufweisen und komplexe makromolekulare Strukturen ausbilden. Für die Funktionalisierung von Polymerketten bietet sich die RAFT-Polymerisation ebenfalls an, da idealerweise jede auf diese Art hergestellte Polymerkette eine RAFT-Einheit trägt und so eine vollständige Funktionalisierung gewährleistet ist. Im Fokus dieser Arbeit stand die Funktionalisierung von Polybutadien und 1,3-Butadien enthaltenden Copolymeren mit gezielt eingebauten schwefelhaltigen Gruppen. Dabei wurden zwei verschiedene Ansätze verfolgt: Die α,ω-Funktionalisierung der Polymerketten mittels modifizierter RAFT-Agenzien sowie eine Funktionalisierung entlang der Polymerkette mit Hilfe von speziellen Monomeren. Da diese Polymere in technischen Anwendungen Verwendung finden sollen, standen einfache Synthesen, die sich gut auf den Technikums- und Industriemaßstab übertragen lassen, im Vordergrund. Da es sich bei der RAFT-Einheit auch um eine schwefelhaltige Gruppe handelt, wurden Strategien zur Funktionalisierung der Abgangsgruppe erarbeitet und experimentell untersucht, um so ein α,ω-funktionalisiertes Polymer zu erhalten. Neben klassischen RAFT-Agenzien wurden auch neuartige Makro-RAFT-Agenzien verwendet, bei denen die schwefelhaltige Gruppe während einer Polymerisation in situ angebunden wird. Darüber hinaus konnten erfolgreich Monomere synthetisiert werden, die wegen ihrer styrolähnlichen Struktur und der Ähnlichkeit der Monomere Styrol und 1,3-Butadien in ihrem Polymerisationsverhalten gut mit 1,3-Butadien copolymerisieren und dabei die schwefelhaltige Gruppe entlang der Polymerkette einbauen. Das Hauptaugenmerk weiterer Untersuchungen lag auf den Copolymerisationseigenschaften der Monomere. Dazu wurden umfangreiche Untersuchungen mit Styrol als Modellsystem für 1,3-Butadien durchgeführt und die gewonnenen Erkenntnisse in einer Copolymerisation der funktionalisierten Monomere mit 1,3-Butadien verifiziert. Es konnte weiterhin gezeigt werden, dass sich schaltbare RAFT-Agenzien für die Synthese von Poly(butadien)-block-poly(vinylacetat) eignen, obwohl es sich um zwei Monomere mit stark unterschiedlichen elektronischen Eigenschaften handelt, die in einer konventionellen radikalischen Polymerisation kein Copolymer bilden würden. Aufgrund der Ähnlichkeit der Monomere Vinylacetat und Ethylen eröffnet dies neue Wege in der kontrollierten radikalischen Polymerisation von Polybutadien-block-polyethylen und erweitert so das Spektrum der unpolaren Monomere in der RAFT-Polymerisation zur Herstellung von Blockcopolymeren.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nesta Dissertação foi utilizado um sistema catalítico Zieger-Natta à base de neodímio para avaliar a influência do agente de halogenação e da razão molar halogênio:Nd sobre a atividade catalítica, a constante de velocidade de propagação, a conversão da polimerização, a microestrutura, a massa molecular e a polidispersão do polibutadieno 1,4-cis. O sistema utilizado era constituído por versatato de neodímio (NdV), hidreto de diisobutilalumínio (DIBAH) e um agente de halogenação. Os agentes halogenantes estudados foram: cloreto de t-butila (t-BuCl), sesquicloreto de etilalumínio (EASC) e cloreto de dietilalumínio (DEAC), em valores de razão molar Cl:Nd que variaram entre 0,5:1 e 5:1 e o dietil-eterato de trifluoreto de boro (BF3.Et2O), na razão molar F:Nd = 3:1. Os polímeros foram caracterizados por espectroscopia na região do infravermelho para determinação da microestrutura e por cromatografia de exclusão por tamanho para determinação das massas moleculares. O teor de unidades 1,4-cis variou de 90 a 98%, a massa molecular numérica média ( ) permaneceu na faixa entre 0,2 e 2x105, e a massa molecular ponderal média ( ) variou de 1,4 a 4x105 / In this Dissertation a catalyst system based on neodymium was employed to evaluate the influence of halogen source and the halogen:Nd molar ratio on the catalyst activity, polymerization constant rate, polymerization conversion, molecular weight characteristics and microstructure of polybutadiene. The catalyst systems were formed by diisobutylaluminium hydride (DIBAH), neodymium versatate (NdV) and a halogen source. The halogenating agents studied were t-butyl chloride (t-BuCl), ethylaluminium sesquichloride (EASC) and diethylaluminium chloride (DEAC) in a nCl:nNd molar ratio in the range from 0,5 to 5, and boron trifluoride diethyl ether (BF3.Et2O). The polymers were characterized by infrared espectroscopy for determining the microstructure and by size exclusion chromatography to obtain the molecular mass characteristics. The cis-1,4 units contents varied from 90 to 98%, the number-average molecular mass ( ) varied from 0,2 to 2x105 and the weight-average molecular mass ( ) varied from 1,4 to 4x105

Orientador: Edson Cocchieri Botelho / Resumo: Esta pesquisa visa o processamento de compósitos termorrígidos laminados multifuncionais, via moldagem por compressão a quente, constituídos por fibras de carbono, resina epóxi e mantas de poli(butadieno) (BR) produzidas via processo de eletrofiação. Estas mantas têm como função proporcionar maior tenacidade ao compósito obtido, aumentando sua tolerância ao dano e consequentemente, elevando sua aplicabilidade no setor aeroespacial. Para o desenvolvimento deste trabalho de pesquisa, primeiramente, foram produzidas mantas de poli(butadieno) por eletrofiação. Todas as condições de processamento foram avaliadas nesta etapa do projeto. Posteriormente, estas mantas foram utilizadas para a obtenção de diferentes compósitos com resina epóxi e fibra de carbono, utilizando-se oito distintas configurações, processados via moldagem por compressão a quente. A qualidade dos compósitos fabricados foi avaliada a partir de ensaios de digestão ácida, microscopia, análise dinâmico mecânica (DMA) e inspeção acústica por ultrassom. Com o intuito de se avaliar eventuais ganhos na tenacidade à fratura dos laminados, foram realizados ensaios de excitação por impulso e resistência ao impacto, o qual foi seguido pela técnica de ultrassom. Também foram realizados ensaios de End-Notched Flexure (ENF) pelo modo II de fratura (modo de deslizamento) e ensaios de cisalhamento interlaminar (ILSS) e após os respectivos ensaios, os compósitos também foram avaliados por microscopia. A partir da técnica de eletr... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This research aims the processing of multifunctional laminated thermosetting composites by hot compression molding, consisting of carbon fibers, epoxy resin and polybutadiene (BR) mats produced by electrospinning. These mats can provide greater toughness to the composite obtained, increasing its damage tolerance and consequently increasing its applicability in the aerospace field. For the development of this research, polybutadiene mats were produced by the electrospinning process. All processing conditions were evaluated at this stage of the project. Subsequently, these mats were used to obtain different epoxy resin/ carbon fiber composites with 8 distinct configurations, processed by hot compression molding process. The quality of the manufactured composites was evaluated using acid digestion tests, microscopy, dynamic mechanical analysis (DMA) and acustic inspection by ultrasound. After processing, in order to evaluate possible gains in fracture toughness, these laminates were submitted impulse excitation tests, impact resistance, and after tests the specimens were analyzed by ultrasound. Also, End-Notched Flexure (ENF) testes were performed using mode II fracture (sliding mode) and interlaminar shear tests (ILSS) and after the respective tests, the composites were also evaluated by microscopy. Using the electrospinning technique, it was possible to manufacture polybutadiene microfibers successfully, and use them to process laminated composites consisting of carbon fibers ... (Complete abstract click electronic access below) / Doutor

Polymers are subjected to physical and chemical changes during their processing, service life, and further recovery, and they may also interact with impurities that can alter their composition. These changes substantially modify the stabilisation mechanisms and mechanical properties of recycled polymers. Detailed knowledge about how the different stages of their life cycle affect the degree of degradation of polymeric materials is important when discussing their further waste recovery possibilities and the performance of recycled plastics. A dual-pronged experimental approach employing multiple processing and thermo-oxidation has been proposed to model the life cycle of recycled high-impact polystyrene (HIPS). Both reprocessing and thermo-oxidative degradation are responsible for coexistent physical and chemical effects (chain scission, crosslinking, apparition of oxidative moieties, polymeric chain rearrangements, and physical ageing) on the microstructure and morphology of polybutadiene (PB) and polystyrene (PS) phases; these effects ultimately influence the long-term stability, and the rheological and mechanical behaviour of HIPS. The PB phase has proved to be the initiation point of HIPS degradation throughout the life cycle. Thermo-oxidation seems to have more severe effects on HIPS properties; therefore, it can be concluded that previous service life may be the part of the life cycle with the greatest influence on the recycling possibilities and performance of HIPS recyclates in second-market applications. The results from the life cycle degradation simulation were compared with those obtained from real samples from a large-scale mechanical recycling plant. A combination of different analytical strategies (thermal analysis, vibrational spectroscopy, and chromatographic analysis) is necessary to obtain a detailed understanding of the quality of recycled HIPS as defined by three key properties: degree of mixing, degree of degradation, and presence of low molecular weight compounds. / QC 20101119

Ce travail de thèse porte sur la synthèse de copolymères greffés à squelette 1,4-polybutadiène (PBu) et polyoxanorbornène par combinaison de ROMP et chimie click et/ou polymérisation RAFT selon la méthode grafting through. Une gamme de macromonomères symétriques et non symétriques originaux poly(oxyde d’éthylène) (POE), poly(acrylate d’éthyle), poly(acrylamide de N-isopropyle) (PNIPAM) et POE-b-PNIPAM ont été synthétisés à partir de précurseurs oxanorbornène et cyclobutène fonctionnalisés présentant un ou deux groupements clickables et/ou un agent RAFT par chimie click et polymérisation RAFT. Une série de PBu-g-POE et polyoxanorbornène-g-POE bien définis ont été obtenus par ROMP en solution en utilisant des amorceurs de Grubbs et de Schrock. Les tests de ROMP en milieu aqueux dispersé ont montré que la mini-émulsion était efficace pour la polymérisation des macromonomères POE à extrémité cyclobutényle et oxanorbornényle. / The objective of this thesis is the preparation and characterization of well-defined graft copolymers with 1,4 polybutadiene (PBu) backbone and polyoxanorbornene backbone by combination of ROMP and “click” reaction and/or RAFT polymerization according to the “grafting through” method. A series of new symmetrical or non-symmetrical poly(ethylene oxide) (PEO), poly(ethyl acrylate), poly(N-isopropylacrylamide) (PNIPAM) and PEO-b-PNIPAM macromonomers was prepared by “click” reaction and/or RAFT polymerization from cyclobutenyl and oxanorbornenyl precursors -containing “click-able” groups and/or a RAFT agent. A series of polyoxanorbornene-g-PEO and PBu-g-PEO with low PDIs has been obtained by ROMP in solution using the Grubbs or the Schrock catalysts. The ROMP in dispersed aqueous media showed that the mini-emulsion conditions were efficient for the polymerization of both oxanorbornenyl- and cyclobutenyl-functionalized PEO macromonomers.

<p>This work investigated the effects of varying the crystal sizes of ammonium perchlorate (AP) when embedded with a polymeric binder, hydroxyl-terminated polybutadiene (HTPB) on impact-induced temperature behavior.  AP and HTPB are the most used oxidizers and fuel binders in the aerospace solid rocket design industry. In this study, samples of 200 µm and 400µm coarse AP crystals in HTPB were constructed using a conventional hand-mixing method. Using a parametric optimization technique such as the Taguchi method, direct-ink-writing as the additive manufacturing process was used for achieving the required shape fidelity in printing HTPB and by introducing ultraviolet polymers to decrease the curing time.</p> <p>A drop hammer experiment in conjunction with an infrared camera was used to study the impact-induced behavior in the conventionally made AP-HTPB samples. The thermal images obtained from the camera at millisecond resolution are invaluable and provide information about distribution across the sample surface, and the evolution of temperature rise observed in the samples which are complex and not easily understood otherwise and therefore help in improving and attaining desired propellant performance. A two-sample t-Test has been utilized to infer the results and statistical nonsignificance has been observed in the highest temperature rises among 200 µm and 400 µm AP-HTPB sample conditions but a difference in temperature distribution has been observed. A much uniform distribution of temperature over the sample surface on impact is observed in thermal images of 200 µm AP-HTPB sample condition compared to 400 µm AP-HTPB sample condition.</p>