This thesis is concerned with the design, synthesis and properties of thermotropic liquid crystals based on the fluorene and 9,10-dihydrophenanthrene core units. Derivatives of 9,10-dihydrophenathrene were found to be both expensive to prepare and difficult to purify, and attention was concentrated on fluorene derivatives. Simple 2,7-disubstituted fluorenes are either monotropic or exhibit enantiotropic smectic phases. Accordingly a third benzene ring was directly coupled to the fluorene core to give a 2-phenylfluorene. The homologous series of 2-(4-cyanophenyl)-7-alkylfluorenes from ethyl to nonyl was prepared via a five step convergent synthesis, and the compounds were isolated as white crystalline solids. All the compounds exhibited enantiotropic nematic phases, and the heptyl, octyl and nonyl homologues also exhibited a smectic A phase. The parent compound 2-(4-cyanophenyl)fluorene with no alkyl chain was prepared by a similar route, but did not exhibit an enantiotropic mesophase. Some physical properties of 2-(4-cyanophenyl)-7-pentylfluorene were measured, and many values {e.g. dielectric anisotropy and birefringence) were similar to those for the commercially successful 4-pentyl-4"-cyano-p-terphenyl. However 2-phenylfluorene material had a higher viscosity. These properties could be related to the crescent shape of the 2-phenylfluorene core, which is dictated by the bridging methylene group. Lateral substitution of the fluorene core was investigated in an attempt to prepare low melting point derivatives. Four C9 alkylated compounds were prepared, and these were found to be oils. However no mesophases were detected. Some 2-(4-alkoxyphenyl)-7-alkylfluorenes were prepared as low birefringence analogues, but these were found to exhibit smectic phases at high temperatures. The analogous alkoxy compound 2-pentoxy-7-(4-cyanophenyl)fluorene was prepared but could not be satisfactorily purified. Preliminary investigations into partial reduction of the fluorene core were carried out, but these did not progress beyond an early stage.

No description available.

No description available.

The synthesis of polyesters and copolyesters containing the bicycl o[2. 2.2]octane ring and 1,4-cycl ohexanedi acetic acid and 1,4-cyclohexanedimethanol spacers are discussed. The following homopolyesters were synthesized: poly[oxy(2-methyll, 4-phenylene)oxycarbonyl-l,4-bicyclo[2.2.2]octylenecarbonyl] I; and poly[oxy(2-chloro-l,4-phenylene)oxycarbonyl-l,4-bicyclo[2.2.2]octy-1 enecarbonyl] II. The following copolyesters were synthesized: poly[oxy (2-chl oro- 1,4-phenyl ene )oxycarbonyl-l ,4-bi cycl o[2. 2. 2]octyl enecarbonyl-co-oxy- (2-chloro-1,4-phenylene)oxysebacoyl] III; poly[oxy(2-methyl-l,4- phenylene)oxycarbonyl-l,4-bicyclo[2.2.2]octylene-co-oxy(2-methyl-l,4- phenyl ene)oxysebacoyl] IV; poly[oxy(2-methyl-l,4-phenylene)oxyterephthaloyl- co-oxy(2-methyl-l,4-phenylene)oxy-l,4-cyclohexanediacetoyl] V; poly[oxy(2-methyl-1,4-phenylene)oxyterephthaloyl-co-oxymethylene-1,4 cyclohexylenemethyleneoxyterephthaloyl] VI; and poly[oxy(2-chloro-1,4 phenylene)oxyterephthaloyl-co-oxymethylene-1,4 cyclohexylenemethyleneoxyterephthaloyl]VII. The resulting homopolyesters and copolyesters were characterized by proton NMR, DSC, TGA, IR, solution viscosity, and polarizing optical microscopy.

No description available.

No description available.

Thermotropic liquid crystalline polymers (TLCPs) have attracted great interest because of the combination of their promising properties, which includes high stiffness and strength, excellent processability, and outstanding chemical resistance. TLCPs exhibit inherently low viscosity relative to many other conventional thermoplastics. The low melt viscosity is detrimental to processes requiring high melt strength, such as extrusion blow molding, film blowing, thermoforming and multilayer coextrusion. Our laboratory has developed a unique method to increase the viscosity of TLCPs by first raising the temperature above the melting point (Tm) to exclude all solid crystalline structure, and then lowering the temperature below Tm to super cool the materials. Additionally, the super-cooling behavior of TLCPs allows them to be blended with other thermoplastics possessing lower processing temperatures. The initial focus of this dissertation is to investigate the processing temperature of a representative TLCP in the super-cooled state, using the methods of small amplitude oscillatory shear (SAOS), the startup of shear flow and differential scanning calorimetry (DSC). The TLCP used in this work is synthesized from 4-hydroxybenzoic acid (HBA), terephthalic acid (TA), hydroquinone (HQ) and hydroquinone derivatives (HQ-derivatives). The TLCP of HBA/TA/HQ/HQ-derivatives has a melting point, Tm, of around 280 oC. Once melted, the TLCP can be cooled 30 oC below the Tm while still maintaining its processability. As the TLCP was cooled to 250 oC, a one order magnitude increase in viscosity was obtained at a shear rate of 0.1 s- 1. Additionally, super cooling the TLCP did not significantly affect the relaxation of shear stress after preshearing. However, the recovery of the transient shear stress in the interrupted shear measurements was suppressed to a great extent in the super-cooled state. The second part of this work is concerned with the extrusion blow molding of polymeric blends containing the TLCP of HBA/TA/HQ/HQ-derivatives and high density polyethylene (HDPE), using a single screw extruder. The blends were processed at a temperature of 260 oC which is 20 oC below Tm of the TLCP such that the thermal degradation of HDPE was minimized. Bottles were successfully produced from the blends containing 10, 20 and 50 wt% TLCP. The TLCP/HDPE blend bottles exhibited an enhanced modulus relative to pure HDPE. However, the improvement in tensile strength was marginal. At 10 and 20 wt% TLCP contents, the TLCP phase existed as platelets, which aligned along the machine direction. A co-continuous morphology was observed for the blend containing 50 wt% TLCP. The preliminary effectiveness of maleic anhydride grafted HDPE (MA-g-HDPE) as a compatibilizer for the TLCP/HDPE system was also studied. The injection molded ternary TLCP/HDPE/MA-g-HDPE blends demonstrated superior mechanical properties over the binary TLCP/HDPE blends, especially in tensile strength. Consequently, it is promising to apply the ternary blends of TLCP/HDPE/MA-g-HDPE in the blow molding process for improved mechanical properties. Finally, this work tends to determine how the isothermal crystallization behavior of a TLCP can be adjusted by blending it with another TLCP of lower melting point. One TLCP (Tm~350 oC) used is a copolyester of HBA/TA/HQ/HQ-derivatives with high HBA content. The other TLCP (Tm~280 oC) is a copolyesteramide of 60 mol% hydroxynaphthoic acid, 20 mol% terephthalic acid and 20 mol% 4-aminophenol. The TLCP/TLCP blends and neat TLCPs were first melted well above their melting points, then cooled to the predetermined temperatures below the melting temperatures at 10 oC/min to monitor the isothermal crystallization. As the content of the low melting TLCP increased in the blends, the temperature at which isothermal crystallization occurred decreased. Comparing with neat TLCPs, the blend of 75% low melting TLCP crystallized at a lower temperature than the pure matrices, and the blend remained as a stable super-cooled fluid in the temperature range from 220 to 280 oC. Under isothermal conditions, differential scanning calorimetry (DSC) was not capable of reliably detecting the the low energy released in the initial stage of crystallization. In contrast, small amplitude oscillatory shear (SAOS) was more sensitive to detecting isothermal crystallization than DSC. / Ph. D.

Du fait de leurs exceptionnelles propriétés, un très vaste champ d'applications s'ouvre aux nanotubes de carbone. La connaissance de leur toxicité est un enjeu primordial afin de connaître les risques et les dangers que ces objets représentent.Le travail présenté dans cette thèse vise à la synthèse de dérivés ayant pour but de favoriser les interactions entre les nanotubes et le milieu vivant.La synthèse d'une série de dérivés du cholestérol utilisables pour la fonctionnalisation des nanotubes de carbone a été mise au point. L'utilisation de tels dérivés a pour but de favoriser les interactions entre les objets greffés et les membranes cellulaires.Par ailleurs, de nombreux intermédiaires de synthèse présentent des propriétés mésomorphes. Celles-ci ont été étudiées au moyen de différentes méthodes telles que la microscopie optique, la calorimétrie différentielle à balayage et la diffusion des rayons X.Des nanotubes HiPco ont pu être purifiés et fonctionnalisés. L'analyse de leur cytotoxicité a été abordée, celle-ci a permis de mettre en avant une diminution de la toxicité des nanotubes greffés comparée à celles de nanotubes purifiés. / Synthesis and study of mesomorphic properties of grafts for carbon nanotubes functionalizationIn order to study the toxicity of carbon nanotubes, cholesterol based derivatives were synthesized. Due to their exceptional properties, a wide field of applications is opened for carbon nanotubes. Regarding this field, knowing their toxicity becomes a key issue.The work presented here aims towards the synthesis of chemical derivatives designed to increase interactions between carbon nanotubes and a biological environment. The synthesis of a series of cholesterol derivatives aimed for the functionalization of carbon nanotubes has been developed. Such derivatives are intended to interact with cell membranes.Moreover, many synthetic intermediates have mesomorphic properties. These properties have been studied using different methods such as polarized optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray scattering (MWAXS).HiPco nanotubes have been purified, functionalized and characterized with techniques such as Raman spectroscopy and X-ray diffraction (XRD).Finally, a study of carbon nanotubes toxicity is presented.

Ph.D. / The specific topic of this investigation is the crystal chemistry and thermotropic polymorphism of the inorganic mineral acid salts of the n-alkyldiamines. This series of compounds contain organic cations with a linear alkane backbone that ranges from short to long chains. As a result their properties changes according to chain length. As they are salts they have the ability to conduct current resulting in wide industrial applications, biological as well as in their use as surfactants and ionic liquids at relatively low temperatures. They also have promising properties for use as propellants, explosives and other pyrotechnic compositions. Their electrical and electronic properties are under investigation. Their ability to exhibit polymorphism has not previously been established. Polymorphism is the ability of a material to exist in more than one crystal form. Since long-chained materials are known to have flexible hydrocarbon chains, by chemical intuition it is reasonable to assume that these materials may have more than one type of molecular arrangement. Various investigations of the conformational and thermotropic polymorphism of the salts of the related n-alkylamines have previously been published in the literature but very little information is available for the polymorphism that may or may not exist in the salts of the n-alkyldiamines. This study is limited to the short and medium chain length n-alkyldiammonium halide salts; nitrate salts; sulphate and perchlorate salts where the general chemical formula for the materials under investigation is CnH2nN+H3X where n = 2 to 12 (except 11) and X = Cl-, Br-, I-, NO3 -, SO4 2- and ClO4 -. It was anticipated that within this range of materials both the hydrogen bonding interactions and the Van der Waal’s forces (as combined packing forces) will play a part in controlling the molecular packing. A large number of the materials were synthesized and their structural information was analyzed by the complimentary techniques of X-ray diffraction and thermal analysis. X-ray diffraction was used in this investigation as it is the best technique to study the crystal chemistry and the polymorphic behaviour of these materials. The results obtained from this method of analysis, the positions of atoms in the crystals, allows for the analysis of the three-dimensional packing in the crystal structure as well as the identification of the hydrogen bonding interactions. The technique of single crystal X-ray diffraction allows the determination of the crystal structures of polymorphs at specific temperatures resulting in information on the effect of change in temperature on crystal packing. Since the compounds investigated in this study were relatively easy to crystallize it was possible to obtain the large single crystals required to obtain single-crystal X-ray diffraction data, and accurate crystal structures could be obtained by this method. Out of a total of thirty-eight crystal structures compared in this investigation, sixteen were novel crystal structures and fourteen were rederminations of previously published structures deemed to be of inferior quality and not suitable for the comparative study. The remaining eight data sets were used as published. Two thermal analytical techniques, Differential Scanning Calorimetry (DSC) and Hot-Stage Microscopy (HSM), were employed to establish if thermotropic phase changes were evident in these materials. Phase transition temperatures at above ambient temperatures were determined by DSC methods while morphological and textural changes in crystals of the compounds under investigation were monitored by HSM methods. In many of the materials analyzed, multiple above ambient phases were identified and only one structure showed a unique below ambient solid-state phase transition.

One portion of this work was concerned with injection molding pregenerated microcomposites composed primarily of poly(ethylene terephthalate) (PET) as the matrix and HX1000 as the thermotropic liquid crystalline polymer (TLCP). Several factors were examined to maximize the mechanical properties of these composites, including injection molding temperature, matrix viscosity, and nozzle tip exit diameter. In addition, concentrated strands of HX1000/PET (50/50 wt%) were diluted using both an injection molding grade of PET and an injection molding grade of PBT. From this work, it was determined that the best mechanical properties were produced when the microcomposites were processed at the lowest injection molding temperatures, diluted with PBT, and injection molded using a large nozzle tip exit diameter. The pregenerated microcomposite properties were compared against theoretical predictions as well as glass-filled PET. It was found that the pregenerated microcomposites had tensile moduli of approximately 70% of theoretical expectations in the machine direction. Additionally, the comparisons against glass-filled PET revealed that at the same weight fraction of reinforcement, the pregenerated microcomposites had lower properties. Still, the composites were found to have smoother surfaces than glass-filled PET and at temperatures up to 150° C the storage and loss moduli of the pregenerated microcomposites were similar to those of glass filled PET. It was concluded that if the theoretically expected levels of reinforcement could be attained, the pregenerated microcomposites processing scheme would be a viable method of producing light weight, wholly thermoplastic composites with smoother surfaces than are obtained with glass reinforcement. An additional focus of this research was to evaluate the ability to modify the crystallization behavior of a high melting TLCP (HX6000, Tm = 332° C) with a lower melting TLCP (HX8000, Tm = 272°C). It was found that it was possible to tailor the crystallization behavior of these TLCP/TLCP blends by varying the weight fraction of each component, as determined by rheological cooling scans and differential scanning calorimetric cooling tests. Based on the analysis of these TLCPs at the maximum injection molding temperature of 360° C, it was speculated that they had reacted with one another. / Ph. D.