Universiẗat, Diss., 2003--Bielefeld.

Orientador: Inez Valeria Pagotto Yoshida / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T14:08:08Z (GMT). No. of bitstreams: 1 Abbehausen_Camilla_M.pdf: 940208 bytes, checksum: 2b2315fde8a813d9a3f372ac94b57962 (MD5) Previous issue date: 2009 / Resumo: No presente trabalho obteve-se híbridos de siloxano e b-ciclodextrina (b-CD). Baseando-se na comprovada reatividade das ciclodextrinas frente a grupos isocianatos, sintetizou-se um híbrido de b-ciclodextrina e siloxano, pela reação da b-ciclodextrina com g-isocianatopropiltrietoxissilano (IPTS), formando uma ligação uretana entre o silano e a b-ciclodextrina. O alcoxissilano, posteriormente hidrolisado, deu origem a um material resinoso do tipo polissilsesquioxano (PSS) modificado por b-ciclodextrina. O mesmo alcoxissilano foi também submetido à condensação com poli(dimetilsiloxano) contendo ¿Si(CH3)2-OH em finais de cadeia, dando origem a uma rede polimérica, também de aspecto resinoso, contendo nos nós de reticulação a b-cyclodextrin. Os materiais obtidos foram caracterizados estruturalmente por espectro infravermelho (IV), ressonância magnética nuclear de C (RMN C) e de Si (RMN Si) e análise por difração de raios X (DRX). O comportamento térmico dos materiais foi analisado por termogravimetria (TGA). A capacidade formadora de complexos de inclusão das ciclodextrinas inseridas no polímero PSS-b-CD foi avaliada pela inclusão de fenolftaleína, monitorada por espectrofotometria na região UV-vis e a difusão de água pelo material foi avaliada por ensaios de intumescimento. A morfologia dos filmes dos materiais preparados foi analisada por microscopia eletrônica de varredura (SEM). / Abstract: In this study, hybrid polymers derived from siloxane and b-cyclodextrin (b-CD) were obtained, by reaction of b-CD with g-isocianatepropyltriethoxysilane (IPTS), forming a urethane bond between these components. The resulting alkoxysilane was hydrolyzed generating b-CD-modified polysilsesquioxane resin (b-CD-PSS). The alkoxysilane was also submitted to condensation with poly(dimethylsiloxane) with ¿ Si(CH3)2-OH end groups, giving rise to a resinous polymeric network. These materials were characterized by infrared spectrum, C and Si nuclear magnetic resonance and X ray diffraction. The thermal behavior was analyzed by thermogravimetry. The capability of b-CD grafted in the siloxane polymers to form inclusion complexes was evaluated by the formation of b-CD-phenolphthalein, by UV-vis sectra. The ability of water diffusion into b-CD-PSS film was evaluated by swelling measurement. b-CD modified siloxanes were able to form films and their morphologies were evaluated by scanning electron microscopy. / Mestrado / Quimica Inorganica / Mestre em Química

Der Schwerpunkt dieser Arbeit lag in der Synthese und Charakterisierung von Sulfonsäure bzw. Sulfon - und Carbonsäure - funktionalisierten Polysiloxanen für die Anwendung als selbstätzendes Dentaladhäsiv. Die grundlegende Aufgabe eines Dentaladhäsivs ist es, eine starke und langzeitstabile Verbindung zwischen Zahnhartsubstanz und Kompositmaterial zu gewährleisten. Aktuell auf dem Markt erhältliche selbstätzende Adhäsivmaterialien können jedoch das enorme Anforderungspaket teilweise nur unzureichend erfüllen. Diese enthalten meist Phosphor- bzw. Phosphonsäure - funktionalisierte Monomere, deren Hauptproblem eine ungenügende Ätzwirkung auf Dentin ist. Monomere mit stärkeren Säuregruppen, wie etwa Sulfonsäuregruppen, beschränken sich momentan auf Acrylamidomethyl-propansulfonsäure, welche lediglich in zwei kommerziell erhältlichen Adhäsivsystemen in geringen Mengen zugesetzt wird. Als Folge dieses aktuellen Forschungsbedarfs befasste sich diese Arbeit mit der Synthese und Charakterisierung neuartiger Sulfonsäure - bzw. Sulfon- und Carbonsäure -funktionalisierter Polysiloxane und der Untersuchung dieser hinsichtlich ihrer Eignung als selbstätzendes Adhäsivmaterial. / The focus of this dissertation is the synthesis and characterization of sulfonic or, respectively sulfonic and carbonic acid functionalized polysiloxanes for dental self -etching adhesives. The primary aim of dental adhesives is to provide a strong and long term stable adhesion to both the composite filling and the dental hard tissue. In addition to withstand mechanical forces a good adhesive should be able to prevent microleakage along the margins, possess a low toxicity and should be easy to use. Conventional dental adhesives based on organic monomer systems are not able to fulfill the requirements sufficiently. Currently used self - etching adhesives contain mostly phosphoric and phosphonic acid functionalized monomers, whose main problem is an insufficient corrosive property on dentin. However, the application of monomers containing stronger acidic groups, for example sulfonic acid, only concerns 2-acrylamidoethylpropane sulfonic acid so far. In this work new sulfonic acid functionalized inorganic - organic polysiloxanes were synthesized and the desired compounds analyzed with regards to their polymerization behavior, their corrosive properties on dental enamel and their bond strengths.

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No description available.

A series of mixed matrix membranes based on zeolites incorporated into fluorinated polyimides were fabricated and characterized in this study. The first system consisted of a polyimide (6FDA-6FpDA-DABA) with carboxylic acid groups incorporated into its backbone and amine-functionalized zeolite particles (ZSM-2). FTIR indicated that these functional groups interacted with each other through hydrogen bonding. Both SEM and TEM images revealed good contact between the polyimide and the zeolite. Permeability studies showed a drop in He permeability suggesting there were no voids between the two components. While simple gases such as O2 and N2 followed effective permeabilities predicted by mixing theories, polar gases such as CO₂ did not. The second system fabricated used the same polyimide with amine-functionalized zeolite L. This zeolite differs from ZSM-2 in that zeolite L's pores are not clogged with an organic template, and it possesses 1-D pores as opposed to ZSM-2's 3-D pore structure. XPS and zeta potential experiments were performed to verify the presence of amine groups on the zeolite surfaces. FTIR data showed that after a heat treatment, amide linkages were created between the amine group on the zeolite and the carboxylic acid group of the polyimide. SEM images showed a good distribution of zeolite L throughout the polymer matrix, and no indication of voids between the two components. Permeability experiments were performed to determine if the addition of zeolite L to the polyimide improved its separation performance. The permeability was unchanged between the pure polyimide membrane and the mixed matrix membrane, suggesting there were no voids present within the matrix. Permeability results of larger gases followed a Maxwell Model. A third system was prepared using a poly(imide siloxane) (6FDA-6FpDA-PDMS) and untreated zeolite L. The primary focus of this investigation was to determine if the addition of the flexible segment would promote direct contact with the zeolite surface and remove the need to amine-functionalize the zeolite. Poly(imide siloxane)s were synthesized at 0, 22, and 41 wt % PDMS as verified using 1H-NMR. FTIR was employed to qualitatively verify the successful imidization of the polymers. SAXS patterns and TEM images did not reveal distinct phases indicative of phase separation, however, AFM images did show the presence of phase separation of the surfaces of the poly(imide siloxane)s. Permeability results showed a decrease in selectivity and an increase in permeability as the wt % of PDMS was increased. Permeabilities and selectivities dropped as the zeolite loading was increased from 0 to 20 wt %. Upon increasing the zeolite loading from 20 to 30 wt %, increases in permeability were observed, but both the permeability and selectivity were still below that of the pure polymer. The final system studied employed the 41 wt % PDMS poly(imide siloxane) as the polymer matrix and either closed-ended or open-ended carbon nanotubes as the filler. SEM images showed regions of agglomeration for both types of nanotubes. Helium permeability dropped in both types MMMs, but more so in closed-ended carbon nanotubes MMM. Nitrogen permeability was unchanged for the closed-ended carbon nanotubes MMM, and dropped slightly in the open-ended carbon-nanotube MMM. / Ph. D.

The research described in this thesis originated from an idea to develop new body protection for the sport of fencing. The ultimate goal is to develop body armour which would be flexible, wearable, washable, light and breathable, offer protection from injuries and cover the entire body of a sportsman. A new material which exhibits shear thickening behaviour has been specially developed for this purpose in the process of this investigation. The material was designed and synthesised as a soft polymeric system which is flexible, chemically stable and able to increase the value of its modulus of elasticity upon impact at a high strain rate, while remaining in its soft gel-like elastomeric state when low strain rate deformation is applied. The polymeric system that has been developed is based on interpenetrating polymeric networks (IPN) of immiscible polyurethane/urea-ester/ether and poly(boron)n(dimethylsiloxane)m (where on average m ≈ 16 n). In addition, as the polydimethylsilane (PDMS) based polymeric system strongly tends to phase separation, the siloxane polymeric network was chemically cross-linked to the polyurethane polymeric network through polyurethane chemical cross-link-bridges. In order to introduce polyurethane cross-links to a siloxane-based polymeric network, some of the attached methyl groups in the PDMS polymeric backbone were substituted by ε-pentanol groups. The resulting polymeric system combines properties of an alternating copolymer with IPN. The actual substitution of the methyl groups of PDMS into alternating ε-pentanol groups was performed by Grignard reaction of trifunctional chlorosilane monomers, magnesium and 1,5-dibromopentane. Chemical analytical techniques like FT-IR, 13C NMR and 1H NMR spectroscopy were used to reveal the chemical structure of the synthesised polymeric network. The mechanical and dynamical properties of the obtained polymeric system were analysed by dynamic mechanical analysis (DMA). This part of the investigation indicated that the novel polymeric system exhibited shear thickening behaviour, but only at a narrow diapason of deformations (i.e., deformations between 2 to 3 % of the length of the sample). At this limited diapason of deformation an effective increase of the modulus of elasticity from 6 MPa (at lower frequencies, i.e., up to ≤6 Hz of the applied oscillating stress) to 65 MPa (at frequencies between 12.5 to 25 Hz) was obtained. However, no increase in the modulus of elasticity was recorded at deformations below 1.5 % or above 3.5 % of length of the sample at the same frequencies (0 to 25Hz) of the applied oscillating stress.

End-functional poly(ether amic acid)s and poly(siloxane imide) multiblock copolymers, comprised of 2,2'-Bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) / meta-phenylene diamine (MPDA) and hexafluoroisopropylidene-2-bis(phthalic acid anhydride) (6FDA) / meta-phenylene diamine (MPDA) polyimide segments, have been prepared and characterized to explore possibilities for controlling interface properties. Incorporation of polydimethylsiloxane (PDMS) components into polyimide backbone structures can yield advantageous properties such as low energy surfaces and low stress interfaces. End-functional BPDA/MPDA poly(amic acid) salts and poly(siloxane amic acid) salts were prepared in methanolic or aqueous tripropylamine solutions. The polymeric salts formed stable water solutions (or dispersions) and imidized in less than 10 minutes at 260°C. The water solubility and rapid imidization times are ideal for on-line processing. Thus, these materials can be used as sizing and interface toughening agents for fiber reinforced composite manufacturing. Epoxy-polyimide networks prepared from the amine functionalized polyimide with DER 331 epoxy resin and diamino diphenylsulfone showed microphase separation (100-300 nm inclusions) by transmission electron microscopy. Slight toughening of the cured epoxy with 9 weight % imide was observed with the imide as the included phase. Epoxy bilayer films of polyimide (amine end-functional and commercial Ultem™) and poly(siloxane imide) multiblock copolymers were prepared to evaluate the polymer-matrix interphase region. Atomic force microscopy (AFM) analysis of the bilayer films showed diffusion at the interphase for the bilayers prepared with the polyimides and the BPADA/MPDA block copolymers containing polyimide continuous phases. Poly(siloxane imide) multiblock copolymers comprised of 6FDA/MPDA polyimide structures are ideal candidates for controlling interfacial properties between silicon substrates layered with thin films for microelectronic applications. These high Tg materials offer an approach for obtaining reduced moisture absorption and low stress interfaces. Evaluation of the refractive indices of the block copolymer films showed a decrease with increasing siloxane content thus suggesting the possibility of lower dielectric constants. The polymer-metal interfacial properties were investigated for films cast on titanium and tantalum substrates. The results suggested a correlation between the surface hydroxyl concentration of the metal oxide layer with the interfacial properties of the cast poly(siloxane imide) block copolymer films. The surface hydroxyls were thought to hydrogen bond with the PDMS component of the block copolymer. Since the titanium substrate has a higher surface hydroxyl concentration than the tantalum, higher silicon concentrations were observed. The melt imidized end-functional polyimides and poly(siloxane imide) block copolymers produced thermally stable materials with 5% weight loss temperatures well above 400°C. However, the block copolymers showed slightly lower 5% weight loss temperatures as a function of siloxane content with a significant increase in char formation. Correlation of the upper glass transition temperatures with the imide segment length was consistent with findings noted for other phase separated randomly segmented block copolymers. Incorporating PDMS into the polyimide backbone structure has an effect on the bulk and surface properties. The bulk properties of the poly(siloxane imide) block copolymers were characterized using TEM. The morphologies were consistent with classical block copolymers. Surface properties of the block copolymer films as a function of PDMS content were investigated using angular dependent X-ray photoelectron spectroscopy at take-off angles of 15, 30, and 45°. Surface enrichment of PDMS content over that of the bulk was observed at all three sampling depths. Further evidence of this siloxane enrichment in the surface was demonstrated with water contact angle analyses. With as little as 5 weight % PDMS (<Mn> = 5000 g/mol) in the block copolymer there was over a 25% increase in the water contact angle over the polyimide control. The surface topography was influenced by the degree of phase separation and was characterized using AFM. The roughness factor was used to represent the data. It was found that the surface roughness increased with increasing PDMS content. / Ph. D.

Durch die Insertion von CO2 in die Si-N-Bindung von Diaminosilanen sind Di(carbamoyloxy)silane zugänglich. Mittels thermischer Zersetzung dieser Insertionsprodukte können Siloxane und entsprechende Harnstoffderivate erhalten werden. In dieser Arbeit wurden die chemischen Reste in diesen Systemen variiert um Siloxane mit verschiedenen Substitutionsmustern zu erhalten. Außerdem wurde das Substituentenaustauschverhalten des System Aminosilan/Carbamoyloxysilan näher untersucht. Dabei konnte die Substanzklasse der Amino(carbamoyloxy)silane nachgewiesen werden. Auch die Adaption der Versuche auf Triaminosilane und Aminodisilane wurde erfolgreich durchgeführt. Dadurch wurden vernetzte Siloxane als Thermolyseprodukte erhalten. Einige Carbamoyloxydisilane bilden zudem fünffach koordiniertes Silicium aus.:Vorwort 1. Einleitung und Motivation 2. Literaturteil (Siloxane/Silikone und Harnstoffe) 3. Diaminosilane 4. CO2-Insertion in Diaminosilane - Synthese von Di(carbamoyloxy)silanen 5. Thermolyse 6. Triaminosilane und Tri(carbamoyloxy)silane 7. Aminodisilane und Carbamoyloxydisilane 8. Zusammenfassung und Ausblick 9. Experimenteller Teil 10. Anhang

Polysiloxanes represent a unique class of synthetic polymers, employing a completely inorganic backbone structure comprised of repeating –(Si–O)n– 'siloxane' main chain linkages. This results in an assortment of diverse properties exclusive to the siloxane bond that clearly distinguish them from the –(C–C)n– backbone of purely organic polymers. Previous work has elucidated a methodology for fabricating flexible and elastic crosslinked poly(dimethyl siloxane) (PDMS) constructs with high Mc through a simultaneous crosslinking and chain-extension methodology. However, these constructs suffer the poor mechanical properties typical of lower molecular weight crosslinked siloxanes (e.g. modulus, tear strength, and strain at break). Filled PDMS networks represent another important class of elastomers in which fillers, namely silica and siloxane-based fillers, impart improved mechanical properties to otherwise weak PDMS networks. This work demonstrates that proper silicon-based reinforcing agent selection (e.g. siloxane-based MQ copolymer nanoparticles) and incorporation provides a synergistic enhancement to mechanical properties, whilst maintaining a low viscosity liquid composition, at high loading content, without the use of co-solvents or heating. Rheological analysis evaluates the viscosity while photorheology and photocalorimetry measurements evaluate rate and extent of curing of the various MQ-loaded formulations, demonstrating theoretical printability up to 40 wt% MQ copolymer nanoparticle incorporation. Dynamic mechanical analysis (DMA) and tensile testing evaluated thermomechanical and mechanical properties of the cured nanocomposites as a function of MQ loading content, demonstrating a 3-fold increase in ultimate stress at 50 wt% MQ copolymer nanoparticle incorporation. VP AM of the 40 wt% MQ-loaded, photo-active PDMS formulation demonstrates facile amenability of photo-active PDMS formulations with high MQ-loading content to 3D printing processes with promising results. PDMS polyureas represent an important class of elastomers with unique properties derived from the synergy between the nonpolar nature, unusual flexibility, and low glass transition temperature (Tg) afforded by the backbone siloxane linkages (-Si-O)n- of PDMS and the exceptional hydrogen bond ordering and strength evoked by the bidentate hydrogen bonding of urea. The work herein presents an improved melt polycondensation synthetic methodology, which strategically harnesses the spontaneous pyrolytic degradation of urea to afford a series of PDMS polyureas via reactions at high temperatures in the presence of telechelic amine-terminated oligomeric poly(dimethyl siloxane) (PDMS1.6k-NH2) and optional 1,3-bis(3-aminopropyl)tetramethyldisiloxane (BATS) chain extender. This melt polycondensation approach uniquely circumvents the accustomed prerequisite of isocyanate monomer, solvent, and metal catalysts to afford isocyanate-free PDMS polyureas using bio-derived urea with the only reaction byproduct being ammonia, a fundamental raw ingredient for agricultural and industrial products. As professed above, reinforcement of polysiloxane materials is ascertained via the incorporation of reinforcing fillers or nanoparticles (typically fumed silica) or blocky or segmented development of polymer chains eliciting microphase separation, in order to cajole the elongation potential of polysiloxanes. Herein, a facile approach is detailed towards the synergistic fortification of PDMS-based materials through a collaborative effort between both primary methods of polysiloxane reinforcement. A novel one-pot methodology towards the facile, in situ incorporation of siloxane-based MQ copolymer nanoparticles into segmented PDMS polyureas to afford MQ-loaded thermoplastic and thermoplastic elastomer PDMS polyureas is detailed. The isocyanate-free melt polycondensation achieves visible melt dispersibility of MQ copolymer nanoparticles (good optical clarity) and affords segmented PDMS polyureas while in the presence of MQ nanoparticles, up to 40 wt% MQ, avoiding post-polymerization solvent based mixing, the only other reported alternative. Incorporation of MQ copolymer nanoparticles into segmented PDMS polyureas provides significant enhancements to modulus and ultimate stress properties: results resemble traditional filler effects and are contrary to previous studies and works discussed in Chapter 2 implementing MQ copolymer nanoparticles into chemically-crosslinked PDMS networks. In situ MQ-loaded, isocyanate-free, segmented PDMS polyureas remain compression moldable, affording transparent, free-standing films. / Master of Science / Polysiloxanes, also referred to as 'silicones' encompass a unique and important class of polymers harboring an inorganic backbone. Polysiloxanes, especially poly(dimethyl siloxane) (PDMS) the flagship polymer of the family, observe widespread utilization throughout industry and academia thanks to a plethora of desirable properties such as their incredible elongation potential, stability to irradiation, and facile chemical tunability. A major complication with the utilization of polysiloxanes for mechanical purposes is their poor resistance to defect propagation and material failure. As a result polysiloxane materials ubiquitously observe reinforcement in some fashion: reinforcement is achieved either through the physical or chemical incorporation of a reinforcing agent, such as fumed silica, or through the implementation of a chemical functionality that facilitates reinforcement via phase separation and strong associative properties, such as hydrogen bonding. This research tackles polysiloxane reinforcement via both of these strategies. Facile chemical modification permits the construction PDMS polymer chains that incorporate hydrogen bonding motifs, which phase separate to afford hydrogen bond-reinforced phases that instill vast improvements to elastic behavior, mechanical and elongation properties, and upper-use temperature. Novel nanocomposite formulation through the incorporation of MQ nanoparticles (which observe widespread usage in cosmetics) facilitate further routes toward improved mechanical and elongation properties. Furthermore, with growing interest in additive manufacturing strategies, which permit the construction of complex geometries via an additive approach (as opposed to conventional manufacturing processes, which require subtractive approaches and are limited in geometric complexity), great interest lies in the capability to additively manufacture polysiloxane-based materials. This work also illustrates the development of an MQ-reinforced polysiloxane system that is amenable to conventional vat photopolymerization additive manufacturing: chemical modification of PDMS polymer chains permits the installation of UV-activatable crosslinking motifs, allowing solid geometries to be constructed from a liquid precursor formulation.