The analysis of the conformation of a stiff-chain polyester by
magnetic birefringence is
presented. The specific Cotton−Mouton constant,
C
2
b, has been measured for five
different molecular
weights of the polyester. A general analysis of the data is
presented, including the effect of polydispersity.
A weak dependence of C
2
b on
molecular weight is found, which shows that the persistence length of
the
polyester is approximately 11 nm. Estimates of the specific
Cotton−Mouton constant per unit length by
using group increments compare favorably with the measured
value.
= 3 , 4 and 5 they are, respectively, 343,316 and 306 K. These parameters that measure the intensities of the orientation-dependent intermolecular interactions are correlated with the optical anisotropy ha and the average intermolecular cohesive energy expressed by the characteristic pressure p *. The characteristic temperature T* decreases slightly with chain length. The lattice theory of nematic fluids is extended to include mixtures of rodlike molecules having different characteristic temperatures T* in order to treat binary and ternary mixtures of the p-oxybenzoate oligomers. The wide biphasic gaps predicted for the several binary systems and the concomitant pronounced partitioning of the components between the nematic and isotropic phases are not confirmed by experiments. Compositions of the coexisting phases in ternary systems were found to be identical within limits of experimental determinations. These marked departures from theory are explicable on the premise that facile rotational diffusion of the nematogens here considered, which are of comparatively low chain length, leads to rapid generation of ordered domains of large dimensions. Subsequent diffusional transport over the required distances consequently is very slow. The transition temperatures observed in binary systems are in excellent agreement with calculations carried out in the "single component" approximation using mean values of the axial ratio and of T* for the mixture, these being taken to be the same in the two phases at equal concentrations.
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