Mesophases, segment conformation

The case of isotactic polypropylene (iPP) presents some differences with respect to those just discussed. While both sPP and PET adopt in their mesophases disordered, extended, essentially non-helical conformations, iPP is characterized by a unique, relatively well ordered, stable chain structure with three-fold helical symmetry [18,19,36]. More accurately we can state that an iPP chain segment can exist in the mesophase either as a left handed or as the enantiomeric right-handed three-fold helix. The two are isoener-getic and will be able to interconvert only through a rather complex, cooperative process. From a morphological point of view Geil has reported that thin films of mesomorphic iPP quenched from the melt to 0 °C consist of... 

The potential of mean torque, parameterized by the local interaction tensors Xa and Xc (assume to be cylindrical) for the aromatic core and the C C segment, respectively, can be mapped out at each temperature by fitting the observed quadrupolar splittings in the mesophase. Furthermore, the order matrix of an average conformer of the molecule can also be calculated.17 Now pn is needed to describe the internal dynamics. 

Collective segmental rotation is considered to be the natural form gaining conformational entropy as the essential factor for stabilizing mesophases or liquid-crystalline structures. Despite the approximate character of our conception it should be possible to identify the significant characteristics of the intermolecular segmental arrangement in mesophases, in liquid crystals or in a polymer melt. 

In 5 (Fig. 4.20) steric hindrance in the peripheral region appears to be too high for formation of a liquid-crystalline phase. Mesophases were characterised by polarisation microscopy and X-ray diffraction. Presumably the LC properties cease as a result of segment mobility with increasing number of stilbene building blocks in principle, the number of conformers should double with each double bond although the maximum number of 2n (e.g. 221 for the third generation) is unattainable for symmetry reasons. 

Our interest here is to review the thermodynamic character of the flexible chain segment which joins the mesogenic cores on both sides in the so-called mainchain liquid crystals. In the LC state, the flexible segments adjust themselves to make them compatible with the environment. The flexible segment thus takes a mesophase conformation which is different from either the isotropic random-coil or the extended crystalline conformation [26,81-87]. 

---