Mesophase reactivity

Mesogenic diols, such as 4,4 -bis( CO-hydtoxyaLkoxy)biphenyls, ate used with 2,4-TDI or 1,4-diisocyanatobenzene (PPDI) to constmct Hquid crystalline polyurethanes (7). Partial replacement of the mesogenic diols by PTMG shows that the use of lower molecular weight flexible spacers form polymers that have a more stable mesophase and exhibit higher crystallinity (8). Another approach to Hquid crystal polyurethanes involves the attachment of cholesterol to the polyurethane chain utilizing the dual reactivity in 2,4-TDI (9). 

In conclusion, we believe that our ability to observe higher atropisoraeric excesses from Irradiations of BN in cholesteric mesophases than from thermal lsomerlzations can be traced to the larger interaction energies associated with the excited state species and its environment. The cumulative effect of these Interactions is manifested more specifically on a reactive solute when the solvent molecules are uniquely ordered than when they are isotropically dispersed. 

Composition of Parent Pitch. Once the chemical composition of the carbonizing system moves away from the comparative simplicity of polynuclear aromatic hydrocarbons to that of industrial pitches, then the pyrolysis chemistry incorporates effects caused by the presence of heteroatoms (0, N and S) and alkyl and naphthenic groups. In general terms, the system becomes more Reactive creating higher concentrations of radicals detectable by ESR. This in turn, leads to enhanced cross-linkages and polymerization of molecular constituents of any mesophase which is formed, and this causes enhanced viscosity and a reduction in size of optical texture. 

This influences the structural features of the mesophase which remains more disordered, a point made by Cranmer et al. (43). Stadelhofer (107) found that the presence of QI did not change rates of formation of mesophase. Romovacek et al. (108) consider that pyrolytic particles in pitch (primary QI) retard the development of mesophase and suppress coalescence. Decrease in size of optical texture, as brought about by mechanical modification as distinct from chemical modification of pitch properties can increase both the strength and reactivity to oxidising gases of the resultant coke, as recently put forward by Markovic et al. (109). ... 

The complexity of formation of mesophase must not be underestimated. With the exception of a few model compounds, it is the industrial pitch which is the source of mesophase. Such materials contain thousands of reactive molecules and there is an interdependence in the carbonization system which currently is known to us but not analyzed in depth. This is an area for further research. Formation of mesophase is further complicated because it involves chemistry within a fluid/plastic system of increasing viscosity. And in the delayed coker, volatile release and liquid turbulence are yet additional factors in influencing final structure in mesophase. 

A major factor to consider in pitch carbonizations is the facility for hydrogen transfer reactions. These stabilize otherwise reactive radical species and permit the growth of mesophase in a fluid of low viscosity. Hydroaromaticity and methylene linkages are able to transfer hydrogen without creating radicals. 

The technology of mesophase-pitch-based carbon fiber has stimulated the rapid development of the chemistry of mesophase behavior and preparation. The carbonization schemes and mechanisms leading to optical anisotropy via the mesophase, the control of carbonization with emphasis on the preparation of spinnable mesophase, and the mesophase transition and reactivity in relation to the structure of its constituent molecules are summarized in this paper. 

In contrast to conventional nematic liquid crystals, the molecular units are disk shaped and range widely in size, even when the mesophase is produced by the pyrolysis of pure organic compounds (17). Many of the molecules are volatile or reactive in the temperature range over which the mesophase is fluid, and the evolution of gaseous species usually causes the mesophase to be extensively deformed by bubble percolation before it congeals to a solid semicoke. 

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