Methods for the large scale preparation and purification of bis( 4-aminopheny 1)-1- phenyl-2,2,2-trifluoroethane (3F-diamine) and bis( 4-hydroxyphenyl)-1-phenyl-2,2,2- trifluoroethane (3F bis-phenol) have been developed. Spectroscopic characterization of by-products was used to develop a mechanistic understanding for synthetic design and to formulate purification techniques needed to produce monomer grade products. Utilizing the preparative methods represented in the present work, it was possible to obtain sufficiently pure 3F-diamine to allow the synthesis of soluble, end-capped, fully cyclized polyimides with glass transition temperatures greater than 430°C. The direct preparation of 3F bis-phenol from phenol and trifluoroacetophenone by trifluoromethanesulfonic acid catalyzed hydroxy alkylation was optimized to produce monomer grade 3F bisphenol. Previously reported methods were less direct and produced lower purity product. Current research efforts are exploring the utility of this monomer system for the preparation of novel poly(arylene ethers), polycarbonates, and polyesters. Bis(4-hydroxy-3- aminophenyI)-1-phenyl-2,2,2-trifluoroethane [3F-bis(aminophenol)] has recently been successfully prepared from 3F-phenol. Soluble, high glass transition temperature, fully-cyclized polybenzoxazoles have been obtained from 3F-bis(aminophenol). The synthesis and characterization of polymer systems containing the phosphine oxide unit as an integral part of the backbone continue to be areas of active research. To date the majority of research activity has centered on the synthesis and features of poly(arylene ether phosphine oxide) (PEPO). All PEPOs gave significant amounts of phosphorus-containing char at temperatures where other engineering polymers are completely volatilized. This behavior was related to the superior self-extinguishing behavior of all the phosphorus containing systems. A detailed pyrolytic degradation study of the phosphorus containing PEPO system was carried out. The study utilized analytical techniques such as pyrolysis-gas chromatography-mass spectroscopy and neutron activation analysis. To continue the exploration of the phosphine oxide systems, the synthesis and characterization of a novel phosphorus containing diamine, bis( 4-amino-phenyl) phenylphosphine oxide, has been completed. Further research is in progress preparing phosphine oxide based polyimides from this diamine. Synthesis of bis(4-hydroxyphenyl)phenylphosphine oxide and additional phosphine oxide intermediates are also reported. / Ph. D.

This thesis has focused on the synthesis and characterization of amino functional monomers, principally monomers containing aryl phosphine oxide units. Utilization of these monomers was demonstrated in various types of linear and network polymerizations. The diamines monomers included bis(3-aminophenyl) methyl phosphine oxide (DAMPO), bis(3-aminophenyl) phenyl phosphine oxide (DAPPO), bis(3-aminophenoxy phenyl) phenyl phosphine oxide (BAPPO) and bis(3-aminophenoxy phenyl) methyl Phosphine oxide (BAMPO). From these monomers high molecular weight poly(ether imides), polyurea-urethanes, poly(arylene ether ketones) poly(arylene ether sulfones) and poly(arylene ether phosphine oxides) were. Internal and external fire testing methodologies showed that the new polymers containing phosphine oxide units were fire resistant while maintaining the desirable physical characteristics of carefully selected control systems. In addition, suitable curing schedules for epoxy networks were determined by using dielectric monitoring techniques. The curing rates varied with the structure of the monomers and were slowest for the deactivated control (4,4'aminophenyl sulfone). Epoxy networks containing aryl phosphine oxide units had higher char yields in dynamic thermogravimetric analyses than control specimens. This correlated with their superior flame resistance. The brittle epoxy matrices were subsequently modified with reactive or non-reactive thermoplastic polymers in order to improve their fracture toughness. Poly(ether imides) and poly(ether sulfones) showed good phase separation behavior with tetrafunctional epoxy matrices during the curing reactions, as confirmed by scanning electron microscopy (SEM) and dynamic mechanical analysis (DMA). Mechanical tests showed that reactive thermoplastic modification of the epoxy networks improved the fracture toughness of the systems, without noticeable decreases in other characteristics such as flexural modulus. Reactive systems also maintained chemical resistance in contrast to non-reactive thermoplastic controls. / Ph. D.

A series of random and amorphous copolyesters containing different cycloaliphatic rings within the polymer chains were prepared by melt polycondensaton of difunctional monomers (diesters and diols) in the presence of a catalyst. These polyesters were characterized by nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), tensile tests and/or dynamic mechanical analysis (DMA). The copolyester based on dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate (DMCD-2) was observed to have a higher Tg, about 115ºC, than the other copolyesters with the same compositions in this study. For copolyesters containing different compositions of dimethyl-1,4-cyclohexane dicarboxylate (DMCD) and DMCD-2, the Tg increased linearly with the increase of DMCD-2 mole content. DMA showed that all of the cycloaliphatic copolyesters had secondary relaxations, resulting from conformational transitions of the cyclohexylene rings. The polyester based on DMCD-3 in the hydrolytic tests underwent the fastest hydrolytic degradation among these samples. A new triptycene diol (TD) was synthesized and incorporated into a series of cycloaliphatic copolyester backbones by melt condensation polymerization. Straight chain aliphatic spacers, including ethylene glycol (EG), 1,4-butanediol (BD) and 1,6-hexanediol (HD), were used as co-diols to explore their effects on polyester properties. An analogous series of non-triptycene copolyesters based on various hydroxyethylated bisphenols were also prepared for comparison. The results revealed that the TD-containing polymers had higher thermal stability and higher Tg's than the corresponding non-TD analogs. For TD-containing copolyesters, the mechanical properties were found to be dependent on the types and compositions of the co-diols. A 1,4-butanediol-based triptycene copolyester was observed to have a significantly increased Tg and modulus while maintaining high elongation at ambient temperature. Furthermore, it was demonstrated that the triptycene polyester exhibited higher Tg and modulus than those containing bisphenol derivatives. However, all of the 1,4-butanediol based copolyesters were brittle and had comparable moduli at low temperatures (-25°C or -40 °C). Melt polycondensation was also used to prepare a series of all-aliphatic block and random copolyesters including the following aliphatic monomers: trans-DMCD, DMCD-2, neopentyl glycol (NPG), diethylene glycol (DEG) and dimethyl succinate (DMS). The polymer compositions were determined by 1H NMR, and the molecular weights were determined using SEC. The polyesters were also characterized by TGA, DSC, DMA and tensile tests. Phase separation was not observed in these block copolyesters. However, the block copolyester containing DMCD-2 and NPG was observed to have a higher Tg than the block copolyester based on trans-DMCD and NPG. In addition, these block copolyesters were found to have better mechanical properties than the corresponding random copolyesters. / Ph. D.

No description available.

O objetivo deste estudo foi avaliar a influência de dois aditivos, propionaldehyde (propanal aldeído) e 2,3-butanedione (diquetona diacetil), nas propriedades de comonômeros, copolímeros e resinas compostas à base de Bis-GMA, quando diluído com TEGDMA, Bis-GMA propoxilado (CH3Bis-GMA) e Bis-GMA propoxilado fluorinado (CF3Bis-GMA). Comonômeros, copolímeros e compósitos experimentais foram preparados combinando Bis-GMA com TEGDMA, CH3Bis-GMA, CF3Bis-GMA e, aldeído (24 e/ou 32 mol%) e diquetona (24 e/ou 32 mol%). No caso dos compósitos, partículas híbridas silanizadas (bário aluminosilicato; 60 peso%) foram adicionadas aos comonômeros. Para a fotopolimerização, adicionou-se canforoquinona (0,2 peso%) e N,N-dimetil-p-toluidina (0,2 peso%). Os comonômeros e copolímeros experimentais tiveram as seguintes propriedades avaliadas: viscosidade, contração de polimerização, grau de conversão, ângulo de contato (em esmalte, dentina e vidro), temperatura de transição vítrea (DSC e equação de Fox), microdureza, alteração de rugosidade superficial e desgaste por abrasão. Os compósitos experimentais, tiveram avaliadas as seguintes propriedades: resistência flexural, módulo de elasticidade, tração diametral, módulo de resiliência, microdureza, alteração de rugosidade superficial e desgaste por abrasão. Os sistemas Bis-GMA/TEGDMA e Bis-GMA/CH3Bis-GMA tiveram suas propriedades significantemente alteradas pela incorporação de aditivos (propanal ou diquetona). Os aditivos (propanal/diquetona) não influenciaram de forma significante as propriedades do sistema Bis-GMA/CF3Bis-GMA. O efeito dos aditivos nas propriedades dos materiais analisados relaciona-se à sua abilidade em aumentar o grau de conversão de alguns sistemas resinosos / The purpose of this study was to evaluate the effect of two additives, propionaldehyde (aldehyde) and 2,3-butanedione (diketone), on the properties of Bis-GMA based comonomer, copolymer and composites when diluted with TEGDMA, propoxylated Bis- GMA (CH3Bis-GMA) and propoxylated fluorinated Bis-GMA (CF3Bis-GMA). Experimental comonomer/copolymer/composites were prepared combining Bis-GMA and TEGDMA, CH3Bis-GMA, CF3Bis-GMA, with aldehyde (24 and/or 32 mol%) and diketone (24 and/or 32 mol%). For composites, hybrid treated filler (barium aluminosilicate glass; 60 wt%) was added to monomer mixtures. Photopolymerization was effected by using camphorquinone (0.2 wt%) and N,N-dimethyl-p-toluidine (0.2 wt%). Experimental comonomer/copolymers viscosity, polymerization shrinkage, degree of conversion, contact angle (enamel, dentin and glass surfaces), glass transition temperature (DSC and Fox equation), microhardness, surface roughness changes and wear were evaluated. Experimental composites, flexural strength, modulus of elasticity, diametral tensile strength, modulus of resilience, microhardness, surface roughness changes and wear were also assessed. Bis-GMA/TEGDMA and Bis- GMA/CH3Bis-GMA systems had properties significantly influenced by incorporation of additives (either propanal or diketone). Additives (propanal/diketone) did not significantly influence on Bis-GMA/CF3Bis-GMA system properties. The effect of additives on the evaluated material properties is mainly attributed to their ability in improving some resin systems degree of conversion

An introduction is given to the background theory and scientific literature of the major subject areas of interest in this thesis, namely the chemistry of free radical and anionic polymerisation, molecular weight control in each type of polymerisation, polymerisation reactors, computer simulation of polymerisation processes and polymer characterisation by gel permeation chromatography. A novel computer model has been devised, based on the analysis of the polymerisation process in terms of the reaction extent of each reactant and the use of generation functions to describe the concentration of living and dead polymeric species, for the free radical, solution polymerisation of methylmethacrylate in a CSTR. Both heat and mass balance expressions have been described. Conversion, Mn and Mw were monitored. To test the model a reactor was designed and constructed. A detailed description of the reactor and the experimental conditions used for the validation of the model are given. The results of these studies are presented and excellent agreement is shown between model predictions and experiments up to 30% conversion for Mn w and % conversion. A similar study is described for the anionic polymerisation of styrene in tetrahydrofuran as solvent, in a CSTR. In this work the computer model becomes 'stiff' when realistic rate constants are introduced in the kinetic expressions. Experimental difficulties were encountered in obtaining reproducible results in the anionic work. A new approach of using 'scavengers' as protecting agents for the living chains is described. A scavenger was successfully employed in the preparation of block copolymers using a tubular reactor. Block copolymerisation, in addition to providing a means of checking the number of the 'living' chains inside the reactor, is of interest in its own right. All the experimental findings are discussed in relation to the currently accepted views found in the scientific literature.

Two new monomers / 2-benzyl-5,12-dihydro-2Hpyrrolo[ 3&rsquo / ,4&rsquo / :2,3][1,4]dioxocino[6,7-b]quinoxaline (DPOQ) and 5,12- dihydrothieno[3&rsquo / ,4&rsquo / :2,3][1,4]dithiocino[6,7-b]quinoxaline (DTTQ), were synthesized. The chemical structures of the monomers were characterized by Nuclear Magnetic Resonance (1H-NMR), Fourier Transform Infrared (FTIR) and Mass Spectrometry (MS). Copolymer of DPOQ with bithiophene (BT) was synthesized via potentiostatic electrochemical polymerization in acetonitrile (ACN)-tetrabutylammonium tetrafluoroborate (TBAFB) solvent-electrolyte couple. For DTTQ, copolymerization with bithiophene was achieved via potentiodynamic method in dichloromethane (DCM)-tetrabutylammonium hexafluorophosphate (TBAFP) solvent-electrolyte couple. Characterizations of the resulting copolymers were performed by cyclic voltammetry (CV), FTIR, Scanning Electron Microscopy (SEM) and UV-Vis Spectroscopy. Four-probe technique was used to measure the conductivities of the samples. Moreover, the spectroelectrochemical and electrochromic properties of the copolymer films were investigated. In addition, dual type polymer electrochromic devices (ECDs) based on P(DPOQ-co-BT) and P(DTTQ-co-BT) with poly(3,4- ethylenedioxythiophene) (PEDOT) were constructed. Spectroelectrochemistry, electrochromic switching and open circuit stability of the devices were studied. They were found to have good switching times, reasonable contrasts and optical memories.

O objetivo deste estudo foi avaliar a influência de dois aditivos, propionaldehyde (propanal aldeído) e 2,3-butanedione (diquetona diacetil), nas propriedades de comonômeros, copolímeros e resinas compostas à base de Bis-GMA, quando diluído com TEGDMA, Bis-GMA propoxilado (CH3Bis-GMA) e Bis-GMA propoxilado fluorinado (CF3Bis-GMA). Comonômeros, copolímeros e compósitos experimentais foram preparados combinando Bis-GMA com TEGDMA, CH3Bis-GMA, CF3Bis-GMA e, aldeído (24 e/ou 32 mol%) e diquetona (24 e/ou 32 mol%). No caso dos compósitos, partículas híbridas silanizadas (bário aluminosilicato; 60 peso%) foram adicionadas aos comonômeros. Para a fotopolimerização, adicionou-se canforoquinona (0,2 peso%) e N,N-dimetil-p-toluidina (0,2 peso%). Os comonômeros e copolímeros experimentais tiveram as seguintes propriedades avaliadas: viscosidade, contração de polimerização, grau de conversão, ângulo de contato (em esmalte, dentina e vidro), temperatura de transição vítrea (DSC e equação de Fox), microdureza, alteração de rugosidade superficial e desgaste por abrasão. Os compósitos experimentais, tiveram avaliadas as seguintes propriedades: resistência flexural, módulo de elasticidade, tração diametral, módulo de resiliência, microdureza, alteração de rugosidade superficial e desgaste por abrasão. Os sistemas Bis-GMA/TEGDMA e Bis-GMA/CH3Bis-GMA tiveram suas propriedades significantemente alteradas pela incorporação de aditivos (propanal ou diquetona). Os aditivos (propanal/diquetona) não influenciaram de forma significante as propriedades do sistema Bis-GMA/CF3Bis-GMA. O efeito dos aditivos nas propriedades dos materiais analisados relaciona-se à sua abilidade em aumentar o grau de conversão de alguns sistemas resinosos / The purpose of this study was to evaluate the effect of two additives, propionaldehyde (aldehyde) and 2,3-butanedione (diketone), on the properties of Bis-GMA based comonomer, copolymer and composites when diluted with TEGDMA, propoxylated Bis- GMA (CH3Bis-GMA) and propoxylated fluorinated Bis-GMA (CF3Bis-GMA). Experimental comonomer/copolymer/composites were prepared combining Bis-GMA and TEGDMA, CH3Bis-GMA, CF3Bis-GMA, with aldehyde (24 and/or 32 mol%) and diketone (24 and/or 32 mol%). For composites, hybrid treated filler (barium aluminosilicate glass; 60 wt%) was added to monomer mixtures. Photopolymerization was effected by using camphorquinone (0.2 wt%) and N,N-dimethyl-p-toluidine (0.2 wt%). Experimental comonomer/copolymers viscosity, polymerization shrinkage, degree of conversion, contact angle (enamel, dentin and glass surfaces), glass transition temperature (DSC and Fox equation), microhardness, surface roughness changes and wear were evaluated. Experimental composites, flexural strength, modulus of elasticity, diametral tensile strength, modulus of resilience, microhardness, surface roughness changes and wear were also assessed. Bis-GMA/TEGDMA and Bis- GMA/CH3Bis-GMA systems had properties significantly influenced by incorporation of additives (either propanal or diketone). Additives (propanal/diketone) did not significantly influence on Bis-GMA/CF3Bis-GMA system properties. The effect of additives on the evaluated material properties is mainly attributed to their ability in improving some resin systems degree of conversion

Résumé confidentiel / Résumé confidentiel

The diploma thesis is focused on the preparation and optimization of molecularly imprinted polymers (MIP) selective for chymotrypsinogen A as well as on the use of these MIP as recognition entities in the sensor. MIP was prepared by suspension polymerization using a mixture of functional methacrylate-based monomers. Prepared MIP was optimized (e.g. binding properties, selectivity and isolation of chymotrypsinogen from a complex matrix of human breath) by capillary electrophoresis with fluorescence detection ( = 532 nm). Finally, the combination of MIP with quartz microbalances was demonstrated as a promising sensor for the detection of proteins from human breath condensate.