Polymer Liquid Crystals
Introduction
Polymer liquid crystals (PLCs) are a class of materials that combine the properties of polymers with those of liquid crystals. These "hybrids" show the same mesophases characteristic of ordinary liquid crystals, yet retain many of the useful and versatile properties of polymers. In order for normally flexible polymers to display liquid crystal characteristics, rod-like or disk-like elements (called mesogens) must be incorporated into their chains. The placement of the mesogens plays a large role in determining the type of PLC that is formed. Mainchain polymer liquid crystals or MC-PLCs are formed when the mesogens are themselves part of the main chain of a polymer. Conversely, side chain polymer liquid crystals or SCPLCs are formed when the mesogens are connected as side chains to the polymer by a flexible "bridge" (called the spacer.)
Other factors influencing the mesomorphic behavior of polymers include the presence of long flexible spacers, a low molecular weight, and regular alternation of rigid and flexible units along the main chain. The following sections will go into greater detail about the structure, phases, and applications of polymer liquid crystals.
Main Chain Polymer Liquid Crystals
Main chain polymer liquid crystals are formed when rigid elements are incorporated into the backbone of normally flexible polymers. These stiff regions along the chain allow the polymer to orient in a manner similar to ordinary liquid crystals, and thus display liquid
crystal characteristics. There are two distinct groups of MC-PLCs, differentiated by the manner in which the stiff regions are formed. The first group of main chain polymer liquid crystals is characterized by stiff, rod-like monomers. These monomers are typically made up of several aromatic rings which provide the necessary size. The following diagram shows an example of this kind of MC-PLC.
The second and more prevalent group of main chain polymer liquid crystals is different because it incorporates a mesogen directly into the chain. The mesogen acts just like the stiff areas in the first group. Generally, the mesogenic units are made up of two or more aromatic rings which provide the necessary restriction on movement that allow the polymer to display liquid crystal properties. The stiffness necessary for liquid crystallinity results from restrictions on rotation caused by steric hindrance and resonance. Another characteristic of the mesogen is its axial ratio. The axial ratio is defined to be the length of the molecule divided by the diameter ( x = L/d ). Experimental results have concluded that these molecules must be at least three times long as they are wide. Otherwise, the molecules are not rod-like enough to display the characteristics of liquid crystals. This group is different from the first in that the mesogens are separated or "decoupled" by a flexible bridge called a spacer. Decoupling of the mesogens provides for independent movement of the molecules which facilitates proper alignment. The following is a diagram of this type of main chain polymer liquid crystal. Notice the flexible spacer (methylene groups) and the stiff mesogen (aromatic ring and double bonds).
Temperature Range Problems
It is difficult to create polymer liquid crystals that show mesogenic behavior over temperature ranges which are convenient to work with. In fact, many times the temperature of the liquid crystalline behavior is actually above the point where the polymer begins to decompose. This problem can be avoided in one or more of the following ways. The first method of lowering polymer melting temperatures involves the arrangement of the monomers in the chain. If the molecules are put together in random orientation (head-totail, head-to-head, etc.), interactions between successive chains are minimized. This allows for a lower melting temperature.
Another method to bring the temperature down to a useful range involves copolymerization. If a random copolymer can be created, the regularity of the chains is greatly reduced. This will help to minimize the interactions between the chains by breaking up the symmetry, which in turn will lower polymer melting temperature. The following picture shows how the irregularity of polymer substituents can lead to decreased interactions.
Finally, defects can be introduced into the chain structure which lower the polymer melting temperature. This method creates 120 degree "kinks" in the chain which disrupt the ability for neighboring polymers to line up. Unfortunately, this also decreases the effective persistence length so too many kinks can destroy any liquid crystal behavior.
Side Chain Polymer Liquid Crystals
It has been demonstrated that main chain polymer liquid crystals often cannot show mesogenic behavior over a wide temperature range (see Main Chain Polymer Liquid Crystals). Side chain polymer liquid crystals, however, are able to expand this scale. These materials are formed when mesogenic units are attached to the polymer as side chains.
Side chain polymer liquid crystals have three major structural components: the backbone, the spacer, and the mesogen. The versatility of SC-PLCs arises because these structures can be varied in a number of ways.
The Backbone
The backbone of a side chain polymer liquid crystal is the element that the side chains are attached to. The structure of the backbone can be very important in determining if the polymer shows liquid crystal behavior. Polymers with rigid backbones typically have high glass transition temperatures, and thus liquid crystal behavior is often difficult to observe. In order to lower this temperature, the polymer backbone can be made more flexible.
The Mesogen
Perhaps the most important part of a side chain polymer liquid crystal is the mesogen. It is the alignment of these groups that causes the liquid crystal behavior. Usually, the mesogen is made up of a rigid core of two or more aromatic rings joined together by a functional group. The following diagram is a typical repeating unit in a side chain polymer liquid crystal. Notice the spacer of methylene units and the mesogen of aromatic rings.
The Spacer
Like their main chain counterparts, mesogens attached as side groups on the backbone of side chain polymer liquid crystals are able to orient because the spacer allows for independent movement. Notice in the following diagram that even though the polymer may be in a tangled conformation, orientation of the mesogens is still possible because of the decoupling action of the spacer.
The structure of the spacer is an important determining factor in side chain polymer liquid crystals. Generally, the spacer consists of two to four methylene (CH2) groups attached together in a line. Accordingly, the spacer length has a profound effect on the temperature
and type of phase transitions. Usually, the glass transition temperature decreases with increasing spacer length. Short spacers tend to lead to nematic phases, while longer spacers lead to smectic phases.
Phases of Polymer Liquid Crystals
Polymer liquid crystals form the same mesophases as ordinary liquid crystals. Understanding the ways in which the molecules line up is important in understanding their properties. Side chain polymer liquid crystals show a tendency to separate the backbone from the mesogenic side groups. This is achieved in the smectic phase where the mesogenic groups and backbone chains form individual layers.
Many side chain polymer liquid crystals form what is known as the "double comb" configuration. This structure is formed when side chains point away from the backbone in an alternating fashion. The double comb configuration allows the polymers to form layers characteristic of the smectic phase.
Atactic polymers in addition to copolymers cannot form this structure because the side chains are connected to the backbone in random directions.
Applications of Polymer Liquid Crystals
Polymer liquid crystals will most certainly become more important as research into this field progresses. Applications for these materials range from the production of highstrength materials to their use in optical devices. The following is an introduction to some of these applications.
High-Strength Fibers
An application of polymer liquid crystals that has been successfully developed for industry is the area of high strength fibers. Kevlar, which is used to make such things as helmets and bullet-proof vests, is just one example of the use of polymer liquid crystals in applications calling for strong, light weight materials. Ordinary polymers have never been able to demonstrate the stiffness necessary to compete against traditional materials like steel. It has been observed that polymers with long straight chains are significantly stronger than their tangled counterparts. Main chain liquid crystal polymers are well-suited to ordering processes. For example, the polymer can be oriented in the desired liquid crystal phase and then quenched to create a highly ordered, strong solid. As these technologies continue to develop, an increasing variety of new materials with strong and light-weight properties will become available.
Optical Applications
The use of polymer liquid crystals in the display industry is an exciting area of research. At this time, PLC's demonstrate relatively slow "response times" to electric fields. That is, when a field is applied, the molecules take a long time to align along it. This is not a good property for use in displays where the screen must be able to change rapidly from one view to another. Researchers are working to overcome this problem because the manipulation of polymers is often much easier than traditional liquid crystals. In applications for which response time is not a factor (or in the future, after response times have improved), a twisted nematic polymer liquid crystal cell can be used to make energy efficient displays. A laser is used to selectively melt portions of the display into the liquid crystal phase. The orientation of the cell is then chosen by applying a field across it, just as in an ordinary twisted nematic liquid crystal cell. When the polymer cools down and hardens into a glass, the mesogens will be locked in that configuration and the field can be turned off. Side chain polymer liquid crystals exhibit good properties for applications in optically nonlinear devices including optical waveguides and electro-optic modulators in poled polymeric slab waveguides. More devices are expected to be fabricated from PLCs in the future: optically-addressed spatial light modulators, tunable notch filters, optical amplifiers, and laser beam deflectors. The properties of ferroelectric chiral smectic C phases make this material useful for films with applications in nonlinear optics.
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