Mainz, Universiẗat, Diss., 2000.

Marburg, Universiẗat, Diss., 2001.

Universiẗat, Diss., 2002--Freiburg (Breisgau).

High temperature polyarylene networks produced through the step-growth thermal cyclopolymerization of mono-ortho-diynylarene (MODA) and bis-ortho-diynylarene (BODA) monomers have been shown to produce high yielding glassy carbon once pyrolyzed at 1000 °C. In this study the homo- and co-polymerization of both monomers will be studied, and the effects of copolymer composition on the processability when applied to carbonization and carbon-carbon composites. The carbon products from these high temperature polymer matrices will also be characterized. MODA and BODA are prepared through a Sonogashira coupling reaction and are polymerized through a heat-initiated Bergman Cyclization reaction mechanism. This work seeks to show how BODA-MODA copolymers can attenuate current composite processing limitations, and improve mechanical properties while retaining high temperature properties including high carbon yields.

No description available.

No description available.

Two novel classes of siloxane containing, organic-inorganic block copolymers were prepared using different synthetic approaches. The first copolymers were alternating poly(arylene ether phosphine oxide)-poly(dimethylsiloxane) systems, prepared via oligomeric silylamine-hydroxyl reactions. Secondly, segmented nylon 6,6-poly(dimethylsiloxane) block copolymers were synthesized via a non-aqueous adaptation of the "nylon 6,6 salt" hydrolytic polyamidization, using bis(aminopropyl) dimethylsiloxane oligomer as a co-reactant. Three series of "perfectly" alternating block copolymers were produced from well characterized hydroxyl-terminated poly(arylene ether phosphine oxide) and dimethylamine-terminated poly(dimethylsiloxane) oligomers, in order to investigate both block length and chemical composition effects. Copolymerization in chlorobenzene resulted in high molecular weight materials capable of forming optically clear, nanophase separated films, which displayed unusual morphologies and good mechanical strength. Thermal gravimetric analysis showed high thermo-oxidative stability and increasing char yield with increasing siloxane content. Additional thermal and mechanical investigations provided evidence of selective phase mixing, particularly at shorter block lengths. Surface analysis showed an enrichment of the siloxane blocks at the air-polymer interface in comparison to the bulk state. This behavior increased in proportion to the length of the parent siloxane oligomers. Evaluation of selected optical properties, e.g., refractive indices, revealed linear trends resulting in values of compositionally weighted averages. Conversely, a series of nylon 6,6-siloxane copolymers were produced from the polycondensation of preformed propylamine-terminated poly(dimethylsiloxane)s, solid nylon 6,6 salt and a corresponding amount of adipic acid to afford siloxane-amide semi-crystalline copolymers with siloxane content ranging from 10 to ~45 wt%. The characterization of high molecular weight and covalent siloxane-amide linkages was hindered by insolubility. For example, crystallinity of the nylon 6,6 precluded the use of common solution techniques, while the susceptibility of the siloxane blocks towards ionic redistribution prevented the use of strongly acidic solvents. However, development of a novel analytical technique using solid state 13C NMR and liquid-solid extraction provided evidence for the presence of covalent bonding between the dissimilar oligomer chains. Thermal gravimetric analysis of resultant copolymers revealed an increase in char yield with increasing siloxane content, a preliminary indicator of increased fire resistance, which was supported by subsequent qualitative Bunsen burner observations. Differential scanning calorimetry showed retention of the polyamide crystalline melt with levels of siloxane incorporation of up to 45 weight %. In conclusion, two novel classes of polydimethylsiloxane containing block copolymers have been successfully synthesized, despite the complications created as a result of the polar/non-polar interactions developed between a semi-inorganic polydimethylsiloxane and the hydrocarbon based polyarylene ethers and nylon 6,6. / Ph. D.

Mechanochromic polymers respond to external force by changing their color. This can be achieved by the incorporation of a molecular switch such as spiropyran (SP) into polymers. SPs can be isomerized by mechanical force from their colorless form into colored merocyanines. Main chain copolymerization of spiropyrans allows investigation of their mechanochromic behavior and potential use as force sensors. So far, several covalent polymer matrices have been used to investigate the mechanochromic response of SPs, among them poly(ε caprolactone) (PCL). Less investigated is how the mechanochromic response can be fine-tuned by substituent effects. First, PCL with differently substituted spiropyrans at the chain’s midpoint were used in order to investigate the effect of different substituents and their regiochemistry on the isomerization behavior of SPs under mechanical stress. A low activation barrier was observed for NO2 substitution of “ortho”-spiropyrans compared to no substitution (R = H). In order to investigate phenyl-substituted “para,para” spiropyrans, a newly developed kinked polyarylene was employed as covalent matrix material. This new polyarylene (PmmpP) has a meta,meta,para connection in its backbone and exhibits excellent mechanical properties. Its high strength allows the isomerization of this molecular switch with a large activation barrier. The phenyl-substituted “para,para” spiropyran showed transient mechanochromism and was switched 25 times in force-and-release cycles. The synthesis of PmmpP was carried out by a Suzuki polycondensation in three steps from commercial starting materials. To further capitalize on the simplicity and properties of PmmpP, a two step synthesis of a semifluorinated kinked polyarylene was demonstrated by direct arylation polycondensation with tetrafluorobenzene (F4). This partially fluorinated PmmpF4 was synthesized with a variety of side-chains. Resulting polymers exhibited a large range of glass transition temperatures, allowing for the production of tailor-made smart materials.