Liquid Crystalline Main Chain Polymers

Properties

In the ideal case of the fully rigid polymer main chain, the longitudinal axes of the macromolecules
are ordered more or less parallel to one another in the nematic melt. The state of order of this long-
range orientation is described through the order parameter S=3/2(=- 1/3) where the angle B gives
the deviation of the longitudinal axis of the molecule from the preferred direction of the longitudinal
axes of all the molecules. For S= 1, all molecules are ordered exactly parallel to one another, and for
the isotropic melt, S=O. The preferred direction of the orientation of the longitudinal molecular axes
is called the director (director = symmetry axis of the orientation distribution function of the
longitudinal molecular axes). The position of the director oscillates due to thermal fluctuations within
a probe so that over the macroscopic dimension of the probe, no single direction of the director
develops.

In reality, unusually high mechanical properties in the fiber direction have been found for these
polymers; however, the theoretically possible values have not been reached. The reason lies in the
imperfect orientation of the director, a degree of order which is less than one (S< I), and the finite
molecular weight of the polymer which leads to defects. In addition, most polymers of this type
crystallize. Theoretically, this should not reduce the mechanical characteristics of the above model,
but apparently the crystallization does heavily influence the mechanical behavior due to defect
structures. Further technological interest in these polymers is based on the lower viscosity of the
nematic phase as compared to the isotropic phase. They are distinguished by their dimensional
stability with a very low thermal expansion coefficient, high temperature stability and low
inflammability. Their possible areas of application extend therefore from fibers and composites to
injection moulded parts of high tolerance with high thermal stability. Tolerance and thermal stability
of electronic and optical components are critical material demands which could be fulfilled by liquid
crystalline main chain polymers.

Liquid Crystalline Side Chain Polymers

Properties

Although the anisotropic phase structure of liquid crystalline main chain polymers results from the
long-range ordering of the main chain, only the mesogenic side groups determine the phase
structure of side chain polymers. Thus the polymer main chain does not itself need to have longrange
ordering. The local chain conformation must only be consistent with the liquid crystalline phase
structure of the side chains. For example, a deformed polymer coil in the nematic phase was
ascertained to have an axial length of 1.5 times its radius of gyration. As a result, these polymers are
similar to conventional amorphous polymers in their mechanical characteristics. They do not show
the unusual mechanical properties of liquid crystalline main chain polymers.

Of special interest is the phase behavior of these polymers when the liquid crystalline melt is cooled
to lower temperatures. This is shown schematically in Figure 7, in which the order parameter S is
given as a function of temperature. With decreasing temperature, the long-range orientational order
of the mesogenic side chain continually increases until a defined temperature Tg,ic below which it
then remains constant. Thermodynamic studies show that at this temperature, the liquid crystalline
melt transforms into the glassy state. Optical and NMR spectroscopic measurements show that the
liquid crystalline structure remains unchanged in the glassy phase. Therefore it is possible to produce
anisotropic glasses which display a nematic or smectic structure depending on the type of polymer.

The glass transition temperature Tg,,= essentially depends on the chemical constitution of the
polymer main chain. A further important aspect is the influence of an electric or magnetic field on
the position of the director in the liquid crystalline phase. In analogy to modern electrooptical display
elements of low molar mass liquid crystals, the position of the director can be changed and
macroscopically ordered by the application of an external field. In the ordered phase, the optical
properties of the polymer correspond to that of a single crystal of the same dimension. By cooling
the polymer into the glassy state, this ordered state is permanently frozen in. The combination of
these characteristics-the glassy state and anisotropic physical characteristics-introduces broad
application perspectives for these polymers as optical components in linear and non-linear
Furthermore, optical memory (storage) elements which can utilize changes in the most diverse
physical properties can be realized. As an example, a recording element which gives high resolution
suitable for holographic photographs is shown in Figure 8.

A uniformly ordered polymer in the glassy state (Fig. 8a) contains a dye which can undergo trans-cis
isomerization. The glassy polymer is warmed into the liquid crystalline state by exposure to a laser
for a short time, and simultaneously the linear trans-dye isomerizes to the bent cis-dye (Fig. 8b). Due
to the bent conformation of the dye, the local ordering of the phase within the radiated area is
reduced, thus changing the anisotropic optical properties. After irradiation, the polymer returns to
the glassy state and the given information is permanently stored. It can be retrieved by a minimal
laser output. The process is reversible (for example, via a thermal reverse reaction to the trans-dye in
the glassy state, in which the local state of order of the phase remains unaffected). A completely
different application follows from the anisotropic properties of the polymer and its negligible vapor
pressure at high temperatures. As stationary phases in gas chromatography such polymers lead to
higher separation efficiencies than conventional material^.

Liquid Crystalline Elastomers

Properties

Elastomers with nematic and smectic phases are known which show the same dependence of the
liquid crystalline phase on the chemical structure of the monomer units as the linear liquid crystalline
polymers. At the glass transition temperature Tg,,= the elastomer freezes into a glass with the liquid
crystalline structure. Of special importance are the mechanical properties of the elastomers. They
behave at higher temperatures in the isotropic phase like conventional rubbers, whereas below the
isotropic-liquid crystalline phase transformation the mechanical properties are direction dependent.
If one considers an undeformed elastomer in the liquid crystalline phase, the preferred direction of
the mesogenic side groups varies due to thermal fluctuations, as it does in low molar mass liquid
crystals and linear liquid crystalline polymers (Fig. 9). If the elastomer is mechanically deformed by a
retractive force, then one obtains a macroscopic ordering of the mesogenic side groups. The
orientation of the mesogenic side groups in the direction of the force is determined by the linkage
between the mesogenic groups and the network. It has thus far been observed that, depending on
the length of the linkage of the flexible spacer, the preferred direction of the longitudinal axes of the
mesogenic groups is either parallel to or perpendicular to the deformation axis; other angular
positions are not found. The elastomer is comparable in its optical properties to a single crystal of the
same dimension. A reorientation results from a change in the direction of the stress, in which the
direction of the stress and the direction of the longrange orientational order are always directly
related. Therefore mechanical deformation of the elastomers has the same influence on the
orientation of the liquid crystalline molecules as an electric or magnetic field has on the orientation
of low molar mass liquid crystals and linear liquid crystalline polymers. Combination of the properties
of anisotropic phase structure, rubber elasticity and the ability to orient the optical axis through
mechanical deformation results in a new class of materials whose scope of application extends
beyond the area of optics. For example, thin anisotropic films can be used as separation membranes.
Other detailed studies on these new materials are therefore not only of theoretical interest with
respect to the interaction between a deformed polymer network and the liquid crystalline phase
structure, but also provide the basis for new applications.
References

https://doi.org/10.1002/anie.198708161