Liquid Crystalline Polymers: Valery Petrovich Shibaev

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Liquid Crystalline Polymers
Chapter · December 2016

DOI: 10.1016/B978-0-12-803581-8.01301-1
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Shibaev V., Liquid Crystalline Polymers. In: Saleem Hashmi (editor-in-chief), Reference Module in Materials Science
and Materials Engineering. Oxford: Elsevier; 2016. pp. 1-46.
ISBN: 978-0-12-803581-8
Copyright © 2016 Elsevier Inc. unless otherwise stated. All rights reserved.
Author's personal copy
Liquid Crystalline Polymers$

V Shibaev, Moscow State University, Moscow, Russia
r 2016 Elsevier Inc. All rights reserved.
1 Introduction 1
1.1 Historical Overview 2
2 Constitution and Structure of Low-Molecular-Mass Liquid Crystals 2
3 LC Polymers: General Consideration 7
4 Main-Chain LC Polymers 9
4.1 Thermotropic LC Polymers 9
4.2 Lyotropic LC Polymers 11
4.3 Properties and Application of LC Main-Chain Polymers 13
5 Side-Chain LC Polymers 15
5.1 Principles of Synthesis 16
5.2 Structural Features of Side-Chain LC Polymers 18
5.2.1 Polymer backbone 19
5.2.2 Spacer length 21
5.2.3 Mesogenic group structure 21
5.2.4 Molecular dynamics 21
6 Properties and Application of Side-Chain LC Polymers 21
6.1 LC Polymers for Passive and Electrically Controllable Optical Elements 22
6.1.1 Nematic LC polymers 22
6.1.2 Cholesteric LC polymers 22
6.2 Photochromic LC Polymers 23
6.3 Chiral-Photochromic LC Polymer Systems 27
6.4 Photo-Responsive LC Polymers as Photo-Optical Sensors 30
6.5 Ionogenic LC Polymers as Self-Assembled and Phase-Microsegregated Liquid Crystals 31
6.6 LC Elastomers 32
6.7 Photomechanical LC Actuators 33
7 LC Block-Copolymers 35
8 LC Dendrimers with Mesogenic Groups 37
9 Liquid Crystals Dispersed in Polymers and LC Composites 38
9.1 PDLCs 38
9.2 Cross-linked LC Polymer Systems 38
9.3 Encapsulated Polymeric Films 39
9.4 LC Composites with QDs 40
10 Miscellaneous LC Polymers 40
11 Conclusion 42
Acknowledgment 43
References 43
1 Introduction
Liquid crystalline (LC) polymers lead one into the heartland of interdisciplinary science embracing the chemistry and physics of
liquid crystals, as well as polymer and materials science. These compounds (composed of an unusual combination of two words –
liquid crystals and polymers) nowadays attract the attention of a wide range of researchers, working in the fields of chemistry, solid
and soft matter physics, biology, medicine, macromolecular science, and nanotechnology. LC polymers are a subject area of a great
☆
Change History: March 2015. Valery Sibaev made the following changes. New eight supplementary sections are added: 6.4, 6.7, 7, 9, 9.1, 9.2, 9.3, and 9.4. A
list of new Figures with their captions was added: Figures 21–45. In Figures 5 and 39 some changes are introduced and Figure 5 a new banana-shaped
molecular structure is included. In Figure 39 two new structural formulas – statistical- and block-denrimers are added. In Figure 27 the diffraction grating
image is included as an insert. The author has made some changes and additions in the next sections: Section 6.2 ‘The photoaligment processes for creation of
the command coatings’ with Figures 21 and 22 are added. In addition to this section some new results concerning holographic gratings and surface relief
gratings (Figures 23, 24) are included. In Section 6.3 two new last paragraphs with modified Figure 27 are included. References 42 new update references
(2013–2015) are added in the body text.
Reference Module in Materials Science and Materials Engineering doi:10.1016/B978-0-12-803581-8.01301-1 1

2 Liquid Crystalline Polymers
upsurge of interest in their own right for engineers and specialists in polymer technology, materials science, and the electronics
industry.1–23
In many aspects, this situation is similar to that of low-molecular-mass liquid crystals, which also combine seemingly two
uncombinative words – liquids and crystals – and, therefore, they are, like LC polymers also very often called hybrid materials or
centaurs of nature.21,23
Hence, it is appropriate to start with the consideration of the structural peculiarities of the molecular constitution and some
properties of low-molecular-mass liquid crystals before considering LC polymers.
1.1 Historical Overview

Since the discovery of liquid crystals more than 100 years have passed. For the first time, they were revealed by the Austrian
botanist Reinitzer (1888), who observed a peculiar thermal behavior of cholesteryl benzoate ester.21,24–27
This crystalline compound melted into a cloudy liquid at 145 1C and then as the temperature rose to 178 1C it suddenly
became clear. This process was completely reversible and when cooling down, the substance transformed into an opaque liquid
and finally became a white solid crystal. Reinitzer was puzzled about this strange behavior of the cholesteryl benzoate and sent the
sample to German physicist Otto Lemann, who later made detailed observations of this compound by means of a polarizing
microscope with a heat stage. He concluded that cholesteryl benzoate in the indicated temperature range must be in a new state of
matter. This opaque state was characterized by a high optical anisotropy but remained liquid and was able to form droplets similar
to an ordinary liquid. A few years later, Lemann named this state of matter as ‘liquid crystal’ (1900). Classic papers from the
history of liquid crystals are presented in Reference 24.
Contrary to the crystal melting point, Tm, the upper transition temperature where the liquid crystal reverts to an isotropic state
was termed as isotropization temperature, Tiso. Since then all substances capable of combining properties of liquid (flow and
drops formation) and crystalline solids (in particular, their anisotropy, such as birefringence) have been designated as ‘liquid
crystals’ or ‘LC’ compounds. LC compounds are named for their ‘mesomorphic’ or ‘mesophase’ (from the Greek word meso
meaning ‘intermediate’) state (Figure 1). Nowadays, the terms liquid crystal, mesomorphic (or mesomorphous) state, and
mesophase are employed almost synonymously. Substances that under suitable conditions form mesophases are referred to as
‘mesogens.’ All terminological definitions relating to liquid crystals and LC polymers are summarized in IUPAC document.28
The understanding of the nature of the LC state, the study of their structural organization, elucidation of the relationship
between the molecular constitution and physical properties of liquid crystals arrived considerably later in the 1940s and 1950s.
However, the majority of researchers found nothing more than theoretical interest in the study of the LC state. The situation
changed sharply at the beginning and middle of the 1960s, when the unique properties of liquid crystals, due to the high
anisotropy and lability of the molecular structure, began to find extensive areas of practical application. The ability of LC
compounds to ‘respond’ rapidly to changes in temperature, mechanical stress, electromagnetic radiation, and even chemical
environment is now widely used for the construction of special thermoindicators, devices for information recording in electronics,
optoelectronics, display technology, and so on. LC televisions, LC monitors of personal computers, and large and small
portable displays for mobile electronic equipment (telephones, games, video and photo apparatus, and personal productivity
tools) are only a part of the technical devices based on liquid crystals. It can now be said without exaggeration that a number of
branches of modern technologies would be unthinkable without the use of liquid crystals.16,21,27
2 Constitution and Structure of Low-Molecular-Mass Liquid Crystals
Some hundreds of thousands of organic substances that can exist in the LC state are known and the number of such compounds is
continuously increasing. The main structure characteristic of LC compounds is the shape anisotropy and the rigidity of their
CH3 CH3 CH3

H3C
CH (CH2)3 CH
CH3
O
C6H5 C O
Tm Tiso
Crystalline LC state Isotropic

state melt
120 130 140 150 160 170 180 190 200

T, °C
145° 179°
Figure 1 The first LC compound – cholesteryl benzoate and diagram showing the temperature range of LC phase.
Liquid Crystalline Polymers 3
Table 1 Some low-molecular-mass liquid crystals forming different LC phases
No Compounds and its structural form Types of liquid crystals and

phase transition temperatures
(1C)
p-Azoxyanisole
1 Cr 116 N 186 I
CH3O N=N OCH3
O
4-pentyl-4’-cyanobiphenyl
2 Cr 22 N 35 I
C5H11 CN
Cholesterylmiristate
3 CH3 CH3 CH3 Cr 71 Sm 79 Ch 85 I

CH (CH2)3 CH
CH3
CH3
CH3 (CH2)12 COO
Derivative of triphenylene
4 R Cr 80 D 122 I
R
R
R= OCO C11H23
R
Derivative of 2-nitroresorcinol
5 O O Cr 85 B 173 I
C C
O O
N NO2 N
CH CH
R R
R= OC12H25
Cr − crystalline state; N, Sm, Ch, D and B − nematic, smectic, cholesteric, discotic and banana LC phases, respectively; I - isotropic melt.
molecules. Table 1 lists some of the most typical representatives of organic compounds capable of forming LC phase within a
certain temperature range.
The vast majority of liquid crystals that transform from crystalline to LC state on heating are based on ‘rod-shaped’ or ‘board
(lath)-shaped’ molecules. Usually, the rod-shaped molecules are named ‘calamitic’ (from the Greek word calamus).
For example, p-azoxyanisole (see Table 1) is a typical LC compound with a nearly linear structure. From a steric point of view,
this is a rigid-rod of length B20 Å . The two benzoate rings are nearly coplanar. The majority of rod-shaped or board (lath)-shaped
liquid crystals have one, two, and even three benzene rings chemically linked directly to each other or via linking units, such as –
CH¼CH–, –CH¼ N–, –NH–CO–, and –COO–, placed in the core structure.
In addition, there exist a special type of LC compounds consisting of relatively flat, ‘disk-shaped molecules,’ which have a rigid
central part and four to eight flexible chains attached to the core with a suitable linkage (Tables 1 and 2).21,29 And finally, in this
century, a novel type of LC phase, a ‘banana mesophase’ formed by banana-shaped molecules, was discovered.30,31
Table 2 demonstrates the various types of the most well known and widespread mesophases consisting of rod-, board (or lath)-
, disk-, and banana-shaped molecules. Depending on the orientational and positional organization of the molecules, these
mesophases can roughly be divided into nematic, smectic, columnar, and bent-core (banana) LC phases.
The rigid parts of a molecule causing the formation of LC phases in low-molecular-mass and LC polymers are defined as the
‘mesogenic groups’ (see Box 1).
Table 2 Main types of variously shaped molecules forming general LC phases
Box 1 Examples of typical mesogenic groups

One of the most common LC phases is the nematic, where the molecules have no positional order, but they have long-range
orientational order. Thus, the molecules flow and their center of mass positions are randomly distributed as in a liquid. Most
nematics are uniaxial: the molecules are orientationally ordered about a common axis defined as the ‘director’ and represented by
the unit vector n (Table 2). It is very important to stress that nematics can be easily aligned by an external magnetic or electric field.
Aligned nematics have the optical properties of uniaxial crystals and this makes them extremely useful in liquid crystal display
technology.
The smectic phases form well-defined layers that can slide over one another in a manner similar to that of soap. In the smectics,
the molecules are thus positionally ordered along one direction. There are several types of smectic mesophases, characterized by a
variety of molecular arrangements within the layers, such as smectic A (SmA), smectic B (SmB), and smectic C (SmC). In the SmA
phase, the mean orientation of the molecules is parallel to the layer normal, whereas in the SmC phase it is tilted (Table 2).
There exists a more complicated situation for ‘board-shaped’ molecules. The mesophase composed of board-shaped molecules
is characterized by long-range ordering of both the longer and the shorter molecular axes. In this case, a biaxial nematic mesophase
is realized (Table 2).
First, we will discuss the banana mesophases and then the discotic mesophases. A mesogen consists of bent or banana-shaped
molecules, in which two mesogenic groups are linked through a semi-rigid group in such a way as not to be collinear (Tables 1
and 2). These bent-core molecules can form an uniaxial N phase or a number of banana (or boomerang)-shaped mesophases, Bi
(where i ¼1, 2, …,8), structures of which are not completely investigated. The structure of some of the phases has been determined
while it remains uncertain for others. It is likely that the current understanding of the phases will undergo refinements. They can
display an uniaxial N phase and also a number of B phases forming some sort of stacked layers of the smectic type. In the latter
case, if the bent-core molecules possess a dipole, their mesophases exhibit interesting ferroelectric and anti-ferroelectric properties
that open possibilities for the practical application of such mesophases consisting of unique geometrical shape of their
molecules.31
Discotic mesophases are exhibited by somewhat larger molecules that have flat disk-like cores containing, as a rule, several
long aliphatic chains (Table 1). These molecules can form two types of packing – discotic nematic, and columnar mesophases.
In the nematic mesophase, disk molecules tend to align with their symmetry axes parallel to each other and have spatial
distribution of their centers of mass (Table 2). Disk-shaped molecules can be assembled in columns packed parallel on a two-
dimensional (2D) lattice symmetry of the columnar packing. One of the major types of the columnar mesophase is shown
in Table 2.21,29
A specific type of liquid crystals is formed by optically active compounds or optically active mixtures. This phase is often called
the ‘cholesteric phase’ because it was first observed for cholesterol derivatives (see Figure 1). Locally a cholesteric is very similar to
a nematic liquid crystal (therefore, it is also called as ‘chiral nematic’ phase). The molecular centers of gravity have no long-range
order but the molecules tend to be parallel to the common axis that defines the director n (Figure 2).
(a) (b) (c)

Z →
→
n n
→ α
n
d
n→
→
n
P
→
n
→
n
→
n
Figure 2 Schematic representations of (a) the molecules and (b) director arrangements in cholesteric phase; (c) is the planar texture.
However, this structure is helicoidal in which the local director processes around the helical axis Z forming a helicoidal
superstructure with helix pitch P corresponding to the turn of the director at an angle of 2π and a period of change in optical
properties d ¼P/2. Hence,
2πd
P¼ ½1
a
where a is the twisting angle of the helix. In some cholesteric liquid crystal systems, the pitch is of the same order as the wavelength
of visible light. The planar-oriented cholesteric phase in which the long axes of the molecules are parallel to each other exhibits
unique optical properties such as selective reflection of circularly polarized light (l) according to the simple eqn [2]:
l¼nP ½2
where n is the average of refractive index of the cholesteric sample. This unique optical property feature is exploited in a number of
optical applications.21,29,32
Thus, all types of liquid crystals are thermodynamically stable over a definite temperature range. In depending on the con-
ditions of LC formation, liquid crystals are divided into two groups. An LC phase formed by heating a solid or cooling an isotropic
liquid is usually called ‘thermotropic liquid crystals.’
There also exist lyotropic liquid crystals consisting of two or more components that exhibit LC properties in a certain con-
centration range. In the lyotropic phases, solvent molecules fill the space around the compounds to provide fluidity to the system.
The lyotropic liquid crystals are usually formed by amphiphilic compounds composed of two ‘immiscible’ hydrophilic and
hydrophobic parts within the same molecule. The essential feature of lyotropic liquid crystals is the formation of molecular
aggregates or micelles as a result of specific interactions involving the amphiphilic molecules and those of the solvent. The
structures are formed through the microphase segregation of two incompatible components on a nanometer scale. Soap is an
everyday example of a lyotropic liquid crystal as well as the aliphatic carbon acids consisting of hydrophilic head ( –COOH group)
and hydrophobic tail.
At low concentrations of amphiphilic compounds, the molecules are dispersed randomly in water without any ordering. At
higher (but still low) concentrations, these molecules are spontaneously assembled into micelles (or vesicles) (Figure 3(a)).
Figure 3 Some typical LC lyotropic structures formed by amphiphlic molecules in water solutions: (a) cylindric micelle; (b) hexagonal packing of
cylindric micells; (c) lamellar liquid crystal; (d) cell membrane consisting of double phospholipid layers (1) and protein molecules (2).
At higher concentration these assemblies become more ordered, forming long cylinders which arrange themselves into a hexagonal
lattice, or a lamellar phase can be formed (Figures 3(b)–3(d)).
Many biological structures also exhibit lyotropic LC phases. In particular, biological membranes and cell membranes are the
typical examples of lyotropic liquid crystals. Their constituent molecules (e.g., phospholipids) form a bilayer structure in which
some proteins, polysaccharides, cholesterol, and other vitally important components are incorporated.
On the one hand, such anisotropic structure of the membranes allows one to protect its internal part from unwanted
external action and, on the other hand, the liquidity of such structure provides the high transport carriers properties of
the cell – permeability, ions transportation, and so on.25 Most important proteins, such as receptors, enzymes, drug, and
hormone molecules, are freely ‘floating’ inside double lipid layers maintaining the vitally important cell functions. Thus,
the LC nature of the cells provides the unique combination of solid and liquid properties of many biological structures in living
organisms.
3 LC Polymers: General Consideration
As it was shown in the previous section, the main feature of low-molecular-mass liquid crystals is predetermined by the existence
of the anisometric molecules – mesogens or mesogenic groups. From this point of view, it is clear that the long flexible macro-
molecules of polymers easily changing their conformations due to heat movement are not favorable to LC phase formation. It is
well known that flexibility (or rigidity) of polymer chain is determined by a Kuhn segment length, l. Flexible polymers are
characterized by the l values in the range 15–50 Å (Figure 4(a)), whereas l values for rigid-chain macromolecules lie in the range
100–1000 Å or even higher (Figure 4(b)).
Polymers with intermediate l values are usually called semi-rigid ones. It should be pointed out that the rigid macromolecules
in which the length of the Kuhn segment of the chain, l, is much greater than the thickness (diameter) of the chain, d, should easily
form an LC phase. Some examples of such compounds are a-helical polypeptides, macromolecules of DNA, aromatic polyamides,
a number of cellulose ethers, and some polyisocyanates. Macromolecules of such polymers can be approximated in the form of
long rods (Figure 4(b)).
In some sense, these macromolecules can be considered as the mesogens. However, the majority of such rigid-rod polymers are
characterized by the high melting points close to the decomposition temperatures, which exclude the formation of LC phases. In
these cases, the anisotropic phase can be formed only in comparatively concentrated solutions forming lyotropic liquid crystals.
A compromise settlement directed on the creation of thermotropic LC polymers is achieved by the chemical bonding of flexible
and rigid-rod fragments in one and the same macromolecule which can have a linear or branched structure (Figures 4(c) and 4
(d)). Like the rigid-rod fragments, the typical anisometric mesogenic fragments of low-molecular-mass liquid crystals are usually
used. In turn, like the flexible fragments, the long aliphatic or oxyaliphatic groups that diminish the macromolecular rigidity are
used to essentially reduce melting points of such LC polymers. These flexible fragments, which are usually called as ‘spacers,’
provide a rather sufficient autonomy and mobility to the rigid mesogenic groups for their cooperative self-organization with LC
phase formation.
(a) (b) (c) (d)
Figure 4 Schematic representation of macromolecules of different rigidity: (a) flexible chains; (b) rigid-rod LC polymers; (c) main-chain LC
polymers with mesogenic groups; (d) side-chain LC polymers with mesogenic groups (comb-shaped LC polymers).
Thermotropic LC polymers belong to a relatively new class of LC compounds. More than three decades have already passed
since the appearance of the first publications devoted to the synthesis and study of thermotropic LC polymers containing
mesogenic groups in both main chains (main-chain LC polymers) (Figure 4(c)) and side branches (side-chain polymers) or comb-
shaped LC polymers (Figure 4(d)). A great number of studies devoted exclusively to LC polymers, including dozens of mono-
graphs, thematic collections of articles, encyclopedias, and review papers, have been published. Some of them are listed in
refs.1–23,28–32 and other papers are cited in appropriate sections of this article.
The study of LC polymers is of interest in its own right, inspired by the need to clarify the nature and specific features of LC state
of macromolecular compounds.33,34 On the other hand, the interest toward this field is accounted for by the possibility of creating
polymeric systems, combining the unique properties of low-molecular-mass liquid crystals and macromolecular compounds,
making it feasible to produce films, fibers, and coatings with extraordinary features. It is well known that the utilization of low-
molecular-mass thermotropic liquid crystals requires special hermetic protective shells (electro-optical cells, microcapsules, etc.)
that maintain their shape and protect LC compounds from external influences. In the case of thermotropic LC polymers, there is
no need for such sandwich-like constructions, because the properties of low-molecular-mass liquid crystals and polymeric body
are combined in a single individual material. This reveals essentially new perspectives for their application.9,14,17–19
Further development of such studies resulted in the self-reinforced plastics based on LC polymers with main-chain mesogenic
groups and laid a foundation for the use of comb-shaped LC polymers as new photoactive materials for optics, optoelectronics,
photonics, holography, display technology, telecommunications systems, and other no-less important areas of modern engi-
neering.9,16–20,35–38
Note that the LC polymers of the first type (Figures 4(b) and 4(c)) are usually classified as ‘construction materials,’ while the
LC polymers of the second type are usually called ‘functional materials’ (Figure 4(d)).
In initial studies devoted to the synthesis of LC polymers, the main attention was focused on the development of various
methods for incorporating only rod-like mesogenic groups, which are responsible for the formation of LC phase, into main and
side branches of polymer chains. Later, other variants of molecular architecture have appeared. Macromolecules of these com-
pounds contain, as a rule, flexible and rigid (mesogenic) fragments (in the form of rods, disks, and boards) chemically linked via
different ways. The most widespread structures of such macromolecules consisting of rigid mesogens located in main chain, side
branches, and their various combinations are illustrated in Figure 5.
Figure 5 Different types of molecular architectures in LC polymers.

4 Main-Chain LC Polymers
The liquid crystallinity in main-chain LC polymers is associated with molecular chains that are uniformly stiffer than those in
conventional polymers. This stiffness or rigidity is usually achieved by increasing the ‘aromatic content’ (e.g., benzene rings) and
connecting the groups so as to increase chain straightness.
4.1 Thermotropic LC Polymers

As illustrated in Figures 4(b) and 4(c), the thermotropic main-chain LC polymers can be obtained from polymers that
contain only rigid-rod units or a combination of rigid-rod and flexible units. The main structural elements of such linear polymers
are composed of benzene or naphthalene rings, or different heterocyclic fragments collinearly linked to one another by such
groups as
O
C C ; CO NH ; C O ; CH=N ; N=N ; O
Two examples of aromatic polyesters poly(4-oxybenzoyl) 1 and poly(p-phenylene terephthalate) 2 are shown below:
O O O
O C O OC C
n n
1 2
These completely rigid-rod-like macromolecules tend to be highly crystalline and intractable with melting points above the
decomposition temperature of the polymers (4450 1C).
The problem with the design of thermotropic LC polymers is to disrupt the regularity of the intractable para-linked aromatic
polymers to the point at which LC behavior is manifest below the decomposition temperature. Only in this case, can the LC
polymer be processed in a fluid-ordered state.
In addition to the flexible spacers, which are usually included into the rigid-rod molecules of the main-chain LC polymers (see
Figures 4(c) and 6), there exist a number of other approaches to obtain LC polymers with the lowest melting temperature for
better processability in the LC state (Figure 6).4,5,21
The general strategy of reducing the rigidity can be achieved by several synthetic routes. First of all, there is the already discussed
method based on the introduction of methylenic groups (spacers) between mesogenic fragments, which was, for the first time,
used by Italian scientists who synthesized main-chain LC polymers on the basis of polyalkanoates containing spacers of the
different length m (Figure 6(a))39:
CH3 CH3
O C=N N=C OCO (CH2)m CO
n
m= 8, 10, 12
3
The second way is based on the combination of the mesogenic fragments of different shape and size to compose the backbone
(Figure 6(b)). The basis of the next route is the introduction of bulky or long substituents into the monomeric units leading to the
disruption of the linear constitution of the main chain, and decreasing melting points and increasing the solubility of LC polymer
(Figure 6(c)).
The introduction of oxygen, or sulfur atoms into the polymeric chains as some sort of hinge makes the macromolecules
more flexible (Figure 6(d)). And finally, the introduction of nonlinear aromatic units (benzene rings with ortho or
meta substituents) acting as kinks is also a very effective method for decreasing the high melting points of rigid-rod polymers
(Figure 6(e)).
(a)
(b)
(c)
(d)
(e)
Figure 6 General approaches to reducing rigidity of macromolecules for improving the bulk tractability of rigid-rod main-chain polymers. (a)
Introduction of flexible fragments (spacers) into the rigid-rod backbone. (b) Introduction of mesogenic fragments of different shape and size. (c)
Introduction of lateral voluminous substituents or aliphatic chains in random fashion. (d) Introduction of hinges groups. (e) Introduction of
nonlinear aromatic units disrupting the linear rigid-rod macromolecular structure (kink fragments).
Some examples of the flexible spacers and chemical groups modifying and disrupting the linear rigid-rod main-chain LC
polymers are shown below.
Flexible spacers R
(CH2)n (CH2O)n Si O
R n
Bulcky mesogens
O O
n
n
Aliphatic side groups (CH2)n CH3 , n= 3-15
Hinge’s elements
X
n
X= O ; S
Kink-fragments O
n
O C
O
All thermotropic main-chain LC polymers are obtained by polycondensation method of different bifunctional compounds
consisting of rigid (mesogenic) and flexible fragments (spacers). Sometimes a transesterification process is used. The latter is
illustrated by the copolymer obtained by liquid inserting oxybenzoate units into poly(ethylene terephthalate).
AcOH
HO C COO (CH2)2 O H + AcO COOH
O n
HO C COO (CH2)2 OOC O H

O n
4
Copolymers consisting of rigid-rod fragments and modifying units are prepared by copolycondensation reactions dissimilar
aromatic bifunctional compounds forming the macromolecules consisting of the monomer units shown above.
4.2 Lyotropic LC Polymers

The majority of thermotropic main-chain LC polymers are characterized by high molecular rigidity (Kuhn segment values are lying
in the range 400–600 Å ), high melting points (400–450 1C), and poor solubility. So far, the polymers discussed in the previous
section have been thermotropic i.e., show liquid crystallinity in a particular temperature range.
Lyotropic polymer systems differ in that the stability of the LC phase is influenced by the addition of a low-molecular-mass
solvent. An important consequence of solvent addition is that LC phase can be obtained with rigid-rod polymers (Figure 4(b))
which would not otherwise show the mesophase at temperatures below that of thermal decomposition. In other words, lyotropic
LC phase formation is a route to melting point reduction of rigid polymers. Lyotropic crystals are formed in a narrow polymer
concentration and of temperature range and their behavior is governed by the laws of phase equilibrium of the solutions.
The possible formation of anisotropic lyotropic LC phase in polymer solutions was predicted even in the late 1940s and mid-
1950s by Onsager and Flory, respectively.40,41 They developed a theory of LC ordering of polymer solutions consisting of rigid rods
molecules and showed that lyotropic nematic liquid crystallinity is a consequence of the chain stiffness and of large overall shape
anisotropy. When the axial ratio of the rod-like chain (l/d) exceeds some critical value, steric repulsions between the rods alone are
sufficient for the formation of the anisotropic (nematic) order in highly concentrated solutions. In other words, anisotropy arises
for purely steric reasons: due to the impossibility of isotropic arrangement of the relatively dense system of anisotropic rigid-rod
molecules (i.e., mesogens).
The theoretical phase diagram for rigid-rod molecules consists of three regions demonstrating an existence of a liquid isotropic
phase, a two-phase region comprising an isotropic and LC phases, and a pure and stable LC phase (Figure 7). There is a critical
volume concentration of polymer vcr in the solvent, below which the solution is isotropic and above which an LC phase forms.
A special feature of the diagram is an existence of a narrow two-phase ‘corridor’ close to the critical concentration vcr,
corresponding to the two-phase region appearance. The critical concentration is rather small – of the order of 5–10% depending
I II
T
III
0 1
Volume polymer fraction
Figure 7 Theoretical phase diagram for the rigid-rod polymer – solvent system. I – isotropic phase; II – anisotropic LC phase; III – LC phase þ
isotropic phase.
on specific molecular structure of polymer and solvent. The general form of this phase diagram was predicated by Flory in 1956
using a two-component lattice model, nearly 20 years before the first experimental observations on lyotropic solutions of
polypeptides appeared. However, the use of such phase diagrams and the further development of Flory theory, given in theoretical
works by Khokhlov, Semenov,42–44 and comprehensive experimental studies by Papkov45 provided a possibility to calculate the
concentration and temperature ranges of an isotropic and LC phases existence for many specific lyotropic LC systems: polymer–
solvent.
Later in the 1960s, the theoretical predictions concerning the formation of anisotropic LC phases in polymer solutions were, for
the first time, experimentally detected in the solutions of polypeptides, cellulose derivatives, whose macromolecules can be
considered as rigid rods with very high Kuhn segment values (AE1000 Å ). However, the investigations of such lyotropic LC
systems had a purely academic character, and nobody was expecting any advantages for their practical use. This situation was
similar to the history of low-molecular-mass liquid crystals, which only found diverse and wide practical applications a hundred
years after their discovery (1888).
Intensive development of applied research activities in the field of lyotropic LC polymer systems was observed in the mid-
1960s and 1970s, when novel families of aromatic polyamides were obtained. These polymers are usually prepared by the
polycondensation of aromatic diacyl dihalide (HalOCAr1COHal) with an aromatic diamine (H2NAr2NH2) in solution, according
to the reaction
2nHHal
n HalOCAr1COHal + n H2NAr2NH2
H NHAr2NHCOAr1CO OH
n
5
Shown in Table 3 are major examples of basic structural components of lyotropic poly(aromatic amide)s that give rise to lyotropic
solutions in specific, often aggressive solvents, such as fuming or concentrated sulfuric acid, halosulfonic acids, and organic amide
solvents, including dimethylacetamide, N-methylpyrrolidone, each containing either lithium or calcium halides.
The concentration at which lyotropic phase is formed depends on the chemical structure and molecular mass of the polymer,
the solvent nature, and the temperature. Generally, the effective concentration is in the range 10–20% by weight of the polymer in
the solvent at room temperature. All polyamides form nematic lyotropic solutions, and the introduction of either a lateral
substituent on the diamine, or of 1,3-phenylene units (in very small amounts) or of flexible spacer (especially poly-methylene
fragments) can increase the solubility of the polymers in the less aggressive solvent.
Among the aromatic polyamides, poly(1,4-benzamide) (PBA) and poly(p-phenylene terephthalamide) (PPTA) were the first
commercial aramid fibers spinned from lyptropic LC solutions.
CO NH CO CO NH NH
n n
PBA PPTA
Both polymers with the trademark ‘Kevlar’ indeed caused a ‘revolution’ in the industrial production of the synthetic fibers.
Developed by DuPont in 1965, this high-strength material was first commercially used in the early 1970s as a replacement for steel
in tires.46
Table 3 Basic structural fragments of lyotropic poly(aromatic amide)s
Aromatic diacid Aromatic diamine
HOOC COOH H 2N NH2
HOOC COOH H 2N NH2
HOOC N=N COOH H 2N N=N NH2

Another important type of polyamides based on heterocyclic derivatives of p-phenylene called poly(p-phenylene
benzobisoxazole) (PBO) were synthesized, for example, according to the following reaction:
HO OH
H2O
HCl
+ HOOC COOH
ClH3N NH3Cl
O O
C C
N N n
PBO
Another, closely related heterocyclic polymer poly(p-phenylene benzobisthiazole) (PBT) has a similar structure but contains
sulfur in its monomeric units.
S S
C C
N N n
PBT
Both PBO and PBT polymers only form lyotropic LC phases in strong polyphosphoric acid at a concentration of polymer
about 5–6%.
The advantage of PBT fibers over ‘Kevlar’ consists of not only the high elastic properties but also the elevated thermal stability.
The temperature for prolonged use of this fiber is 350 1C, which is 100 1C higher than that for ‘Kevlar’.14,15
4.3 Properties and Application of LC Main-Chain Polymers

The main peculiarities of thermotropic and lyotropic main-chain LC polymers are determined by the existence of rigid-rod-like
macromolecules that spontaneously produce a high anisotropic ordering of polymer chains. Namely, a strong tendency to
self-orientation (or self-organization) of macromolecules along the chain axis provides the basis for the creation of a novel
generation of high-strength, high-modulus fibers and plastics.
Another favorable property of these LC polymers is their high glass transition temperatures (laying, as a rule, above 100 1C) and
high melting points, making these materials more heat-resistant and applicable in higher temperatures than other ordinary flexible
polymers. In the case of the flexible polymers, to achieve maximum tensile strength and high modulus, the polymer molecules had
to be in extended-chain conformation and almost perfect crystalline packing. With flexible-chain polymers, such as polyester or
nylon, this could be accomplished only by mechanically drawing the fiber after melt spinning.
In 1965, researchers at DuPont discovered a new method of producing an almost perfect polymer chain extension. The
polymers PBA and PPTA were found to form lyotropic LC solutions due to rigidity of their macromolecules.
The key structural requirement for the backbone of such macromolecules is the para-orientation on the benzene rings, which
allows the formation of rod-like molecular structures.
To illustrate the difference between LC polymers and flexible, ‘melt’ polymers, let us consider what happens when rod-like
polymer molecules are dissolved, as opposed to molecules with flexible chains (Figure 8).
Flexible-chain polymers have random coil conformations in isotropic solution (or in a melt), and even increasing the polymer
concentration cannot generate a higher degree of order. In contrast, with rigid polymers, as the concentration increases, the rod-like
macromolecules begin to associate in a parallel alignment forming a LC lyotropic nematic phase. LC polymer solutions display
unique new possibilities in fiber manufacturing and processing. Under shear forces, as the solutions pass through a spinneret, the
randomly oriented domains and macromolecules become fully oriented in the direction of the shear. The higly oriented supra-
molecular structure is almost entirely preserved as spin filament structure due to very slow relaxation of the shear-induced
orientation.
For the above polymers, DuPont launched the commercial production of high-strength and high-modulus ‘Kevlar’ fibers and
the Akzo Nobel corporation began production of ‘Twaron’ fibers. In the former, USSR scientists from the Fiber Research Institute
(a) (b)
Figure 8 Scheme of the shear-induced orientation of (a) flexible and (b) rigid rode macromolecules passed through a spinneret. Arrows indicate
the direction of shear.
Table 4 Mechanical properties of some ultrastrong aramid fibers obtained from lyotropic LC polymers
Index Kevlar-49 (USA) Arenka (Tvaron) (Holland) Terlon (USSR)

1
Breaking strength (CN Tex ) 254 190 250–260
Initial modulus (GPa) 130 125 140–150
Elongation at break (%) 2.8 2.7–3.7 2.0–4.0
Density (kg m3) 1450 1450 1450
(Khimvolokno) synthesized high-modulus ‘Terlon’ and ‘Vniivlon’ fibers by fiber spinning from lyotropic solutions of aromatic
copolyamides. Some mechanical properties of aromatic amides produced by different companies are presented in Table 4.46,47
It is important to stress that the physical and, in particular, the mechanical properties of the aramid fibers are essentially dependent
on the past history of the conditions of heat treatment and drawing of the fibers. Data presented in Table 4 give some averaged values
for the aramid fibers produced by different companies. As is seen all these fibers have very high breaking strength and modulus.
‘Kevlar’ and other aramid fibers are characterized by a high resistance to fatigue failure, which is very important for the different
areas of application. All aramid fibers are characterized by the crystalline structure with high melting points (400–450 1C) and they
are resistant to most chemical reagents except for strong mineral acids and bases. The most common solvents such as acetone,
petroleum benzene, petroleum oils, and fuels do not affect the properties of these fibers.
Rigid-chain heterocyclic polymers, such as PBT and PPTA, have a significantly higher modulus of elasticity, attaining 300 GPa,
that is, 2–3 times higher than the modulus of elasticity for Kevlar-49 fiber. This value of the modulus is comparable to the value for
many natural fibers, which is of great practical and theoretical interest. The strength of PBT fibers can attain 4.2 GPa with a high
thermal stability characterized by preservation of the mechanical characteristics up to 370 1C. Brief use of PBT is possible even at
700 1C. Another LC heterocyclic polyarylene PPTA has the modulus of elasticity in extension even higher up to 470 GPa.
The successful use of lyotropic LC systems for the preparation of ultrahigh-strength and high-modulus aramide fibers has
triggered the further search for new thermotropic LC polymers that can be processed without the use of solvents. Such thermo-
tropic systems were prepared from aromatic polyesters, whose macromolecules consist of linearly substituted aromatic rings linked
by ester groups. Numerous LC polymers produced in the 1980s displayed order in the melt phase analogous to that exhibited by
low-molecular-mass liquid crystals.
Poly-p-phenylene terephthalate (PPT) and poly-phydroxybenzoate (PHB) are the simplest and most accessible representatives
of the aromatic polymers:
O OCO CO O CO
n n
PPT PHB
These polymers like polyamides have high melting points, which exceed the temperatures of their thermal decomposition. In
contrast to aromatic polyamides, they do not dissolve without decomposing in any of the known solvents.
In order to decrease the melting points of such polyesters and facilitate their processing through the melt, the copolymerization
of the different bifunctional monomers with their random distribution in the macromolecules are usually used. A particular good
example of the efficiency of random copolymerization in reducing the melting point is provided by the system based on p-
hydroxybenzoic acid (HB) and equal amounts of terephthalic acid (TA) and p-p’-biphenol (B)
O O O
C O C C O O
1-n n
n 2
HB TA B
This copolymer called ‘Xydar’ (Dartco Co., USA) has a rather high melting point of 380 1C with a mole fraction of PHB units of
0.33 and presents a moldable LC polymer.
Another important thermotropic system is based on random copolymers of p-HB and hydroxynaphthoic acid (HNA).
O O
C O C
n O
n
HB HNA
On the basis of these copolymers, the specific types of moldable copolymers known as the ‘Vectra’ series were obtained and first
commercialized in 1983. Processing of ‘Xydar’ and ‘Vectra’ copolymers from LC state gives rise not only to fibers but also to
injected materials.15,47
‘Vectra’ LC polymers are highly crystalline thermotropic (melt-orienting) thermoplastics with high mechanical properties as a
consequence of the self-reinforcing properties derived from the macromolecular orientation in the mesophase. The majority of
melt-extruded LC polyesters have a modulus in the range of 60–70 GPa, a tensile strength of 700 MPa and elongation at break of
1.5–2% in the longitudinal direction.15
The important feature of LC polyesters is a low coefficient of thermal expansion ar1 106 grad1 that is comparable with the
value for inorganic glasses (5 107 grad1) and significantly less in comparison with ordinary polymers (1 104 grad1). These
properties have led to the use of ‘Vectra’ LC polymers in many electronic applications such as sockets, switches, bobbins,
connectors, chip carriers, and sensors. ‘Vectra’ LC polymers have replaced stainless steel in medical applications. The LC polyesters
are particularly attractive for microwave frequency electronics due to low relative dielectric constants, low dissipation factors, and
the commercial availability of laminates.
5 Side-Chain LC Polymers
Another key direction in the field of mesophase polymers is the synthesis and study of functional thermotropic LC systems based
on side-chain (comb-shaped) macromolecules containing long aliphatic branching –(CH2)n –CH3 (n¼4–21) in each main-chain
monomer unit (Figure 9).
The specific structure of such macromolecules, characterized by both mobility of the side chains and their ordering ability,
allowed one to use these polymers as self-organizing systems and convenient polymeric matrices for the creation of LC polymers
that were called ‘comb-shaped LC polymers.’ Long aliphatic spacers chemically linked to mesogenic group (Figure 4(d)) provide
sufficient autonomy to side branches for the formation of diverse types of LC phases. The first attempts to obtain LC polymers via
the synthesis of polymer with mesogenic groups directly linked to the backbone (without spacer) failed1–3 because of noticeable
steric hindrances and conformation restrictions imposed by main chains on the packing of side mesogenic groups.
O CO NH
OC C O
O O
CH2
Figure 9 Schematic molecular structure of a side-chain (comb-shaped) polymer.

The concept of spacers was proposed, for the first time, in studies by Plate, Shibaev, and Freidzon in the middle of the
1970s.1,48–50 As early as 1976, Soviet scientists received a patent for the method of synthesizing cholesterol-containing comb-
shaped LC polymers.49 In 1977, Shibaev and Plate published their comprehensive review on thermotropic LC polymers,1 in which
they presented a detailed justification of the spacer concept, describing various principles of the preparation of LC comb-shaped
polymers, and analyzed unsuccessful attempts of the synthesis of such systems. A little bit later in 1978, the German scientists
Finkelmann, Ringsdorf, and Wendorff published a paper,51 in which the spacer concept was also considered and the method of
synthesizing several comb-shaped LC polymers, which the authors called ‘side-chain liquid crystal polymers,’ was described.
Subsequently, this approach was verified and developed in numerous works performed in many laboratories across the world
and has became a commonly accepted method for synthesis of thermotropic LC polymers with side mesogenic groups, or comb-
shaped LC polymers.1–21,38
5.1 Principles of Synthesis

Three major significantly different methods of preparation of comb-shaped LC polymers can be distinguished:
1. Synthesis of monomers with mesogenic groups and their subsequent homopolymerization (Figure 10(a)) or copolymerization
(Figure 10(b)) with other mesogenic or nonmesogenic compounds (Figure 10(c)).
2. The second method of LC polymer synthesis is based on chemical linking of mesogens containing functional groups to the
polymer functionalized main chain by polymer analogous reaction. However, this method is used much less frequently than
the first one due to the difficulty in obtaining polymers with a 100% degree of substitution and the possible compositional
inhomogeneity of the products formed (Figure 10(d)).
A slightly different but widely used variant of this method is a hydrosilylation reaction between reactive polysiloxanes and
the mesogenic monomers of the olefin type, which can be used for LC polysiloxanes:
CH3 CH3
Pt(Cat)
Si O + CH2=CH Si O
H n n
(CH2) p-2 (CH2) p
R R
(d)
(a)
(b)
(c)
Figure 10 Synthesis of LC polymers with mesogenic side groups: (a) homopolymerization; (b) copolymerization of different mesogenic
monomers; (c) copolymerization of mesogenic and nonmesogenic monomers; (d) polymer analogous reaction: A and B – functional groups.
(a) (b)
(c) (d)
Me = Li, Na, Rb, Cu, Co, Ni
Figure 11 Schematic molecular structures of (a) hydrogen- and (b) ionic-bonded LC polymers as well as (c) LC ionomers, and (d) LC ionophoric
copolymers, containing a crown-ether terminal group.
where R is a mesogenic group. The ease of this method is due to the possibility of obtaining LC polymers with a given degree of
polymerization (DP), n, which is determined by the selection of the starting commercially produced reactive polysiloxanes.
This method is usually used for the preparation of LC elastomers (see Section 6.5) and has also been extended to synthesis of
LC dendrimers on the basis of their carbosilane derivatives (see Section 7).
3. The third group of methods of LC polymer preparation is based on the use of condensation reactions. In this case, so-called
combined polymers containing mesogenic groups in both the main and the side chains can be obtained.
All these methods lead to the formation of the covalently-bonded LC homopolymers and copolymers.
Another group is composed of hydrogen-or ion-bonded LC polymers, where mesogenic groups are attached to the main chains
of homopolymers or copolymers containing functional groups capable of hydrogen or ionic bonding (Figure 11).
A special group of LC polymers is formed by LC ionomers: comb-shaped copolymers of mesogen-containing monomer units
with unsaturated acids, in which a part of the carboxyl groups is replaced with metal ions.52
A closely related group of LC substances is formed by ionophoric LC polymers with side crown-ether groups, which were first
synthesized by Percec.53 The effect of ionophores is based on their ability to form complexes with cations of alkali and alkali-earth
metals transported through biological membranes. This phenomenon opens fascinating possibilities for the creation of new
synthetic anisotropic membranes and sensors that are based on ionophoric LC polymers.54,55
Of certain interest are polymer LC networks and elastomers which have been much studied experimentally in various countries,
especially Germany (Finkelmann et al.);56,57 an excellent series of theoretical studies was performed by Warner and Terent’ev (UK)
and published in their book.58 Polymer LC networks are usually prepared via the copolymerization reaction of mono-and
bifunctional LC monomers or via hydrosilylation of polysiloxane oligomers (Figure 12(a)). Another method of preparing
polymer networks relies on the use of mesogenic low-molecular-mass compounds that form intermolecular cross-linking bridges
(Figure 12(b)).
At the present time, the attention of researchers is aimed at the synthesis of polymer systems with a more complex architecture,
where, in addition to mesogenic groups, other moieties featuring their own functional properties are being introduced into
macromolecules.38 A hypothetical macromolecule of a comb-shaped LC polymer containing (1) mesogenic, (2) chiral, (3)
photochromic, (4) electroactive, and (5) reactive functional groups capable of hydrogen bonding or complexing is schematically
shown in Figure 13.
Mesogenic groups, which quantitatively dominate in a given system and determine the capability of the polymer for self-
organization and formation of the LC phase, are the key structural elements of such a macromolecule. Each of the other molecular
groups (taken either separately or in combination with other groups) imparts exactly those functional properties to the final
(a) (b)
Figure 12 Schemes of (a) covalently-bonded and (b) hydrogen-bonded LC polymer networks.
1 2 3 4 5
Figure 13 A hypothetical macromolecule of a multifunctional polymer containing (1) mesogenic, (2) chiral, (3) photochromic, (4) electroactive,
and (5) reactive functional groups.
material that, at the request of researchers, should be exhibited by the LC polymer: photochromic, electric, chiral (optically active),
ionophoric, or other properties.38
Another version of multifunctional branched LC polymers is LC dendrimers containing mesogenic and other molecular
fragments in ball-shaped molecules and block-copolymers of the different molecular architecture, which are briefly considered in
Section 7.52–55
Thus, the presence of functional groups with various structures strongly affects all the physicochemical properties of these self-
organized anisotropic materials and thus makes it possible to design multifunctional materials, one of the most important
tendencies of modern materials science.
5.2 Structural Features of Side-Chain LC Polymers

The main peculiarity of comb-shaped LC polymers is defined by their dual nature. Actually, the polymer chains are the ‘bearers of
polymeric qualities’ with their ability to form polymeric films, fibers, and coatings, while the side rigid mesogenic groups are
‘bearers of mesomorphic properties.’ In other words, there is a strong ‘antagonism’ (competition) between a tendency of a flexible
polymer chain to its adoption of random coil conformation and a high tendency of rigid mesogenic groups to be ordered in any
structural types of mesophases. Despite this antagonism, the LC ordering and thermodynamically stable LC phase formation of all
three known types can occur in LC polymers: nematic, smectic, and cholesteric. The theoretical considerations of LC phase
formation in comb-shaped and main-chain polymers consisting of flexible- and rigid-chain fragments are mainly presented in
publications given by Warner,59 Khokhlov,44,60,61 Birshtein,62 and other authors.
Thus, although LC polymers contain rather flexible main chains, they can form all three main types of LC structures
(Section 2), namely the nematic structure, characterized only by the orientational order (Figure 14(a)); the smectic structure
accompanied by development of the layered structure (Figures 14(a) and 14(b)); and finally, the so-called cholesteric helical
structure, which appears when chiral moieties in the form of monomer units (red fragments in Figure 14(c)) exist in the
macromolecules.
However, the existence of main chains in LC polymers determines one of the most important peculiarities of these LC
compounds that is shown in Figure 15. The LC state is realized in the temperature interval between glass transition temperature Tg
(or melting Tm, if a polymer crystallizes) and the isotropization temperature Tiso, above which the LC polymer loses its LC
properties and transforms into an isotropic melt. In this temperature interval, the LC polymer behaves as a low-molecular-mass
liquid crystal and gives rises to nematic (N), smectic (Sm), or Chol mesophases.
(a) (b) (c)
P/2
Nematic structure Smectic structure

N* Sm
Cholesteric (chiral nematic) helical structure

Chol
Figure 14 Basic structural types of mesophases of side-chain LC polymers. P is the helix pitch.
Orientation of LC polymer
under the effect of an
external field (E, H, )
Frozen oriented Tg LC phase T iso Isotropic

LC structure (mesophase) phase
(new materials)
Figure 15 Scheme illustrating an existence of LC phase in comb-shaped polymers and its use for obtaining new materials with the frozen LC
structure.
Naturally, the viscosity of the LC polymer in these mesophases is much higher than that of ordinary low-molecular-mass liquid
crystals. Nevertheless, the polymer sample may be easily exposed to an external (electric, magnetic, or mechanical) field with the
concomitant formation of the oriented structure. In this case, the external electric or mechanical fields mostly affect side mesogenic
groups, whereas stretching of the polymer leads to orientation of main chains, while side groups may arrange parallel to,
perpendicularly to, or at another angle to the direction of the orienting field, depending on the type of mesophase.34 It is most
interesting that, when the sample is cooled below Tg, the polymer retains the frozen structure inherent in the nematic, smectic, or
cholesteric LC phase with preservation of those anisotropic properties that were imparted to it in the mesophase under effect of an
external field. The scheme described above vividly demonstrates how the LC structure can be fixed in a solid glassy polymer. This
feature of LC polymers has an extremely fascinating potential for the design of new materials with a unique complex of optical and
other physicochemical properties.
Since the 1970s, thousands of comb-shaped LC polymers of the various molecular constitution (Figure 5) exhibiting the
properties of all major types of mesophases inherent to low-molecular-mass liquid crystals have been synthesized. The funda-
mental relationships between the molecular structure of the LC polymers (molar mass, flexibility of main chain, spacer length, and
chemical structure of the mesogenic group) and the type of the mesophase being formed have been comprehensively described in
a large number of books, reviews, and proceedings.1–21,30,38
Here, we will give attention only to the short consideration of the role of three essential structural components of comb-shaped
polymers – a polymer backbone, a flexible spacer, and a mesogenic group.
5.2.1 Polymer backbone

The existence of the backbone in LC polymers leads as a rule to a sharp improvement of the thermal stability of the mesophase due
to increase in isotropization temperature Tiso. Figure 16 shows a comparison of transition temperatures of low-molecular-mass
alkoxycyanobiphenyls and different comb-shaped LC polymers with identical mesogenic groups. It is clearly seen that the
(1, 1’)
180 CH3
1’ Si O
T, oC n
(CH2)m O CN
2’
140
(2, 2’)
3’
CH2 CH
n
100 OCO (CH2)m O CN
4
(3, 3’)
5 CH3
60
CH2 C
n
3 OCO (CH2)m O CN
2
20
1 (4, 5)
0 2 4 6 8 10 12
m CnH 2n+1 O CN
Figure 16 (1–3) Glass transition, (1–3, 4) clearing and (5) melting temperatures of polysiloxanes, polyacrylates, polymethacrylates, and
alkoxycyanobiphenyls as a function of carbon atoms (m) in the aliphatic spacer. Shaded region shows a temperature range of LC phase existence.
(Adapted from the book ‘Liquid Crystalline and Mesomorphic Polymers’ (Eds. Valery Shibaev and Lui Lam) Springer-Verlag New York, 1994;
Figure 3.4.11)
temperature range for the existence of the mesophases is significantly broader for LC polymers than for their low-molecular-mass
LC analogs.34
The significant role in the mesophase formation also belongs to the flexibility of the macromolecules. As a rule, an increase in
the backbone flexibility in going from polymethacrylates to polysiloxanes for the three series of polymers with the same cya-
nobiphenyl groups and similar spacer length leads to an increase in Tcl (Figure 16).
In general, the transition temperatures Tiso and mesophase melting points, for example, between Sm and N phase, are
considered to be dependent on molecular mass starting from a critical value of DP. If, in the case of oligomers, a rise in Tiso is
evident and the limiting values of this temperature are attained even at small DP (E10) without any change in the type of the
mesophase, then, for higher DP, its values affect not only Tiso but also the type of mesophase being formed.
Figure 17 shows the effect of the DP (P W ) on phase transitions of narrow molecular mass fractions of acrylic polymers with
buthoxyphenyl benzoate groups.
CH2 CH
n
COO (CH2)5 COO OOC OC4H9
It is clearly seen from Figure 17, at low DP, the nematic structure mostly appears, whereas at higher DP, more ordered smectic A
structure and the so-called reentrant nematic Nre, as well as smectic ribbon phase SmС ~ arise. These facts are very important because
neglecting the influence of the DP on the types of mesophases, especially if nonfractionated samples are used for physical studies,
will lead to erroneous interpretation of the experimental data.
The question of the conformational state and packing of the main chains of comb-shaped LC polymers is not completely
established. This situation is explained by the many difficulties related to the synthesis of narrow fractions of the deuterated LC
polymers and to the use of the high-resolution small-angle neutron scattering (SANS) method, as well as to the orientation of the
polymer samples in a strong magnetic field equal to 7–10 T. According to SANS data, one can suggest that the main chain of comb-
shaped LC polymers in a nematic phase presumably tends to assume the prolate conformation where mesogenic groups are
arranged parallel to each other along the backbone long axis. In this case, the ratio of radii of gyration for macromolecules of
comb-shaped polymers oriented in magnetic field H in parallel R8 and perpendicular R> direction should be less than 1 (i.e.,
R8/R> o1, prolate conformation). At the same time, in the smectic phase, the main chains orient predominantly perpendicularly
to the long axis of mesogenic group, localized between the smectic layers, adopting oblate conformation, so that the ratio R>/R8
should be greater than 1 (i.e., R>/R8 41 oblate conformation).
160 I
T, °C
120 SmA
N
80
Nre
~
Sm C
40
G
0 25 50 75 100 320 340
Pw
Figure 17 Effect of the DP (P W ) on phase transitions in fractions of LC polymers 6; SmС ~ is the smectic (ribbon-like) C phase; SmA is the
smectic A phase; N is the nematic phase; Nre is the reentrant nematic phase; and I is the isotropic melt. (Adapted from the paper ‘Frustrated
Behavior of a Side-Chain Liquid Crystalline Polyacrylate’ published in Macromol. Chem. Phys., 2001, 202, pp. 297–303; Figure 2.)
The question about the conformations of main chains in many side-chain and main-chain LC polymers remains unsolved for
various types of mesophases. Without a doubt, this problem is of prime importance for the consideration of an adequate model
treating the packing of all structural elements of such LC polymers. This model is necessary for optimization of the molecular
design and synthesis of LC polymers with desired optical and other physicochemical properties.
5.2.2 Spacer length

The flexible bridge, so-called spacer, which binds the mesogenic groups to the main chain performs several functions. The first
function is to ensure autonomy in the behavior of the mesogenic side groups which are mainly responsible for the mesophase
formation. Another no-less important function of the spacer is its plasticizing effect on the polymer. An increase in the length of
the aliphatic bridge results in a decrease in the Tg, which is the lower temperature boundary of the LC state (Figure 16). Finally,
another equally important function of the spacer group is its effect on the type of mesophase. It is usually possible to pass from the
nematic to the smectic mesophase by increasing the number of methylene units in the spacer.
5.2.3 Mesogenic group structure

The majority of comb-shaped LC polymers have the mesogens attached longitudinally to the backbone with the spacer attached to
one end. In this case, predominantly the smectic phase is obtained. An alternative approach is to attach the spacer to the center of
the mesogen so it is oriented laterally to the main chain (Figure 5). This reduces the tendency for the formation of smectic phases,
and nematic phases are normally obtained irrespective of the spacer length. At the present time, actually any mesogenic group can
be more or less incorporated within a comb-shaped polymer as a pendant side group.
5.2.4 Molecular dynamics

The information on molecular order and dynamics of LC polymers is usually obtained by a combination of methods which
complement each other, such as Nuclear Magnetic Resonance (NMR) and broadband dielectric spectroscopy.63,64 Proton NMR
(2H-NMR) is especially suitable in this field, because after selective labeling the different fragments of the molecule (backbone,
spacer, and mesogenic group) can be monitored separately.
In side-chain LC polymers, the molecular dynamics of the mesogenic groups is decoupled from the main chain by use of a
flexible (aliphatic) spacer. Three relaxation processes typically take place. (1) The β-relaxation which is assigned to librational
fluctuation of the mesogen around the long molecular axis. (2) The δ-relaxation process corresponding to librational fluctuation
around the short molecular axis. (3) And finally, the a-relaxation process corresponds to the motion of the polymer backbone at
the dynamical glass transition. It should be pointed out that below the glass transition some local processes, depending on the
chemical structure of the mesogenic groups and their terminal groups, can be found.64
6 Properties and Application of Side-Chain LC Polymers
The great potential of side-chain LC polymers has not yet been fully realized on a large scale. Nevertheless, their anisotropy nature
and easy orientation in shear, magnetic, or electric fields, combined with the ability to preserve the specific oriented structure in the
solid (glassy) state of the polymer, make them at the present time very attractive in a variety of application areas, such as optics and
electro-optics, information and display technologies, photonics, and sensorics for the creation of a new generation of field-
responsive smart materials. Some of the most important properties of the LC polymers associated with their use in the above-
mentioned areas of application are presented below.
I, %
100
u=0
50
u≠0
0
5 10 15 T, s
Figure 18 Kinetic curve of decrease in the light intensity (in crossed polarizers) of LC nematic polymer film on application of an electric field and
scheme of mesogenic groups orientation of comb-shaped macromolecules.
6.1 LC Polymers for Passive and Electrically Controllable Optical Elements

Let us consider the use of LC polymers for obtaining a number of optical elements based on nematic and cholesteric LC polymers.
6.1.1 Nematic LC polymers

One of the major principles of polymer application is associated with the possibility of using the frozen-oriented LC structure
which can be obtained in an LC polymer sample undergoing the action of external fields in the mobile nematic LC phase
(Figure 15). In such a way, the mesogenic groups can be oriented under the action of electric or magnetic fields leading to a high
orientation of mesogenic groups which will determine the optical properties of polymer films.
Such solid polymeric films with planar (long axes of mesogenic groups parallel to the plane of the film) or homeotropic
orientation (long axes of mesogenic groups perpendicular to the film surface) present the passive optical elements and can be used
for obtaining so-called phase plates or retarders, characterized by their high optical anisotropy. Phase plates used in optics are
usually prepared from crystal quartz or uniaxially stretched films of some polymers. When compared with these materials, the
optical anisotropy of LC polymers is far greater (0.10–0.25 as against 103–102), permitting the use of thinner LC films in many
portable optical devices.
In addition, it is necessary to emphasize that the optical properties of LC polymers can be easily controlled by using an electric
field. Figure 18 shows the generalized kinetic curve of decrease in the light intensity (in crossed polarizers) of the LC polymer film
on application of an electric field. It is seen how the unoriented polydomain opaque polymer film is transformed into the
monodomain sample with homeotropic orientation of mesogenic groups (see scheme in the same Figure 18). In this case, for any
LC polymer with the positive dielectric anisotropy (De40), the orientation of side groups coincides with the direction of the
electric field and the firection of liquid crystal, formed by mesogenic groups. An orientation time depends to a large extent on the
DP, that is, the molecular mass of a polymer and the orientation conditions, such as temperature and electric field voltage. Using
an LC polymer with negative values of De one can obtain the planar orientation of the mesogenic groups which can be fixed in the
glassy state.
Using electric fields, the voltage of which changes along the plane of the polymer film, one can create electrocontrollable thin-
film elements such as a phase cylindrical and spherical lens, as well as a phase diffraction lattice with a specific period of the
domain structure. Some principles of design of such devices are presented in ref. 10.
6.1.2 Cholesteric LC polymers

A necessary condition for the formation of the cholesteric mesophase, or chiral nematic phase, is the presence of a chiral center
chemically bound to the molecules or an optically active additive. Such a center determines the helical twisting mesogens in both
low-molecular-mass and polymeric liquid crystals. Wide opportunities for the synthesis of cholesteric polymers are provided by
the copolymerization of nematogenic and chiral monomers (Figure 19).
Chiral copolymers
CH2=CH CH2 CH CH2 CH
CH2=CH 2
* Copolymerization
*
+
CH2=CH CH2 CH CH2 CH
1
3
* *
Figure 19 Synthesis of chiral LC copolymers by copolymerization of (1) nematogenic monomer with (2) chiral mesogenic monomer, and with (3)
chiral nonmesogenic monomers; chirality of monomers is marked by asterisk.
By varying the chemical structure and compositions of LC copolymers, a wide series of cholesteric polymers with unique optical
properties have been obtained and studied.2,38,65–67 Of most interest is the planar texture of cholesteric compounds (see Figure 2
(c)). In this texture, the direction of the director is parallel to the plane of the layer, while the direction of the helix axis Z is
perpendicular to this plate. This supramolecular helical structure is characterized by selective light reflection (SLR), which (see eqn
[1]) reflects incident light as a common diffraction grating. The region of SLR usually lies in the range 300–105 nm (depending on
the chemical nature and composition of LC copolymers) covering thus the UV-, visible-, and IR-spectral regions.
Within the SLR region, one circular component of natural light that coincides with the sign of helical (right-hand or left-hand)
cholesteric structure is reflected, while another component passes through the sample and does not interact with it. Thus, a
polymer film having the cholesteric structure may serve as a ‘selective circular polarizer’. This is a considerable advantage of LC
polymers when compared with low-molecular-mass liquid crystals for their use in practice.
In addition, the planar helical supramolecular structure of cholesterics possesses the abnormally high specific rotation of the
plane of light polarization, which is as high as 103–104 degree mm1.
Particular emphasis should be placed on the preparation and studies of oligomeric cholesteric cyclic siloxanes containing
cholesterol (Chol) and various mesogenic fragments (R), such as binaphol phenyl benzoate, azobenzene derivatives.68
CH3 CH3
Si O Si O n= 2-4
n
(CH2)3 (CH2)3
1 R= COO Chol
OR OR
Using these compounds and photopolymerizable chiral mesogenic monomers, Silicon Wacker (Germany) and Celex Tech-
nologies (USA) launched the production of cross-linked LC polymers in the form of cholesteric flakes with the whole color range
of the visible spectral region.68 They developed methods for manufacturing reflective interference cholesteric LC pigments (the size
and thickness of particles were 30–50 and 1–5 mm, respectively) for a great diversity of applications – light reflecting coatings and
painting of various domestic items (mobile phones and even cars). Transparent dyes and inks based on these pigments possessed
all the circular polarization properties of cholesterics but since they are invisible to the naked eye they can be used for printing and
recording latent images, for protection and marking of documents, bank notes, securities, and so on.
Currently available polymer cholesterics and pigments offer wide possibilities for designing new types of optical materials that
can be used for the manufacture of the following items. Among them, light filters and reflectors of circularly polarized light with
narrow (30–50 nm) and wide (100–700 nm) spectral regions in the range 350–2000 nm or above. A combination of narrowband
reflective filters and broadband polarizers may be efficiently integrated into the modern technique of preparing LC displays and
may significantly improve their brightness and reduce their manufacturing cost.
6.2 Photochromic LC Polymers

The design of such systems is based on the incorporation of photoactive dye (chromophore) molecules into macromolecules of
LC polymers, and these dye molecules undergo reversible or irreversible chemical transformations under the action of light, such
as E–Z (trans–cis) isomerization, cyclization, dimerization, cross-linking, and polymerization reactions.
Photochromic LC polymers are usually synthesized via the copolymerization of mesogenic monomers with photochromic
mesogenic or nonmesogenic monomers similar to the synthesis of chiral LC polymers (Figure 19), but, instead of a chiral
monomer, a photochromic monomer is used; as a rule, its concentration varies from 10 to 60 mol%. Diverse derivatives of
azobenzene, spiropyran, diarylethenes, cinnamates, and coumarin-containing derivatives are used as photoactive fragments.
The majority of the published papers, reviews, and several books are related to the photochromic azobenzene-containing LC
polymers.69–75,17,76–81 Under polarized UV-light exposure, azobenzene side groups of the nematic or amorphous polymers
(a)
h
(b)
trans cis trans
N
N
N=N N
N
N
N
N
(c)
P∞ cos 2 α > 0, Δn = 0 P∞ cos 2 α > 0, Δn ~ 0.2 − 0.3

Figure 20 Schematic representation of (a) the appearance of photoinduced anisotropy in films of azobenzene-containing polymers leading to
orientation of photochromic and mesogenic groups; (b) trans–cis–trans isomerization of azobenzene groups; and (c) change in the direction of
director n relative to the electric vector of the light wavelength, E, during photo-orientation.
undergo the cyclic processes of trans–cis–trans isomerization that lead to cooperative orientation of mesogenic and even non-
mesogenic groups that orient perpendicularly to the electric vector of a light wave (Figures 20(a) and 20(b)).
As is seen from Figure 20(c), the probability of photon absorption P by azobenzene groups is directly proportional to the
squared cosine of angle a between the direction of electric vector of incident light, E, and the direction of director n of the polymer
sample. These photo-orientation processes inevitably lead to the appearance of the high photoinduced birefringence Dnind falling
in the range 0.2–0.3.
This effect makes it possible to use the difference in the values of n of initial and irradiated samples for recording latent
information and images that are invisible to the naked eye under ordinary conditions but easily readable in polarized light. The
distinctive feature of all azobenzene-containing polymers is that the values of Dnind can be evenly tuned. In image recording, this
phenomenon permits realization of the entire grayscale, and not only to record but also to erase the recorded image owing to a
change in the direction of the polarization plane of writing and erasing beams.68,69 These reversible films are characterized by high
resolution (800–1000 lines mm1), and high recording capacity up to 109 bit cm2.
In addition, the azobenzene-containing copolymers attract significant interest as the most suitable objects for holographic
recording. In accordance with estimates of the scientific bulletin ‘Research’ (Bayer, Germany), the record of the three-dimensional
(3D) image on a holographic compact disc based on azopolymers may be a high as 1000 Gbt. The cost of one bit of information
for photo-optical recording is a factor of B50 less than that in the case of magneto-optical recording.82 There is no question that,
Figure 21 Scheme of LC photoalignment technique using photochromic side-chain polymer PAzo4M as aligning ‘command’ surface. (Adapted
from the paper Liquid crystals photoalignment by films of side-chain azobenzene-containing polymers with different molecular structure.
(Bobrovsky, A., Ryabchun, A., Shibaev, V.P.) J.Photochem. & Photobiol.A: Chem. (2011) 218, 137–142, Scheme 1.84)
with the optimization of the photo-optical properties of polymer materials, they will gradually appear in the market and will gain
various application areas.
Apart from the azobenzene-containing copolymers based on E–Z isomerization processes, a number of coumarin-containing
copolymers can be also used. In this case, the exposure of initial films to UV-polarized light causes development of intermolecular
cycles and thus stabilizes the formation of anisotropic networks. These films are characterized by high dichroism (D¼0.7–0.8) and
excellent thermal stability (up to 250 1C). Therefore, they can be used for the manufacture of retarders, orienting coatings, and
pixilated films for optoelectronics.38,83
The creation of orienting coatings named usually as ‘command’ surfaces for photoalignment of low-molecular-mass liquid
crystals is one of the most important direction in display technologies. Up to now, the orientation of liquid crystals in LC cells in
display technologies is based on the method of rubbing glass plates are plastic substrates covered with a thin LC layer.16–18
Usually, the current-carrying electrodes (based on indium oxide or another material) evaporated on a glass substrate is covered
with a thin polyimide layer, which is rubbed with a special cloth with the use of a special mechanical device. This simple method is
extensively applied in display technologies, despite the obvious limitations: electrostatic charge on the substrate surface, surface
contamination due to the rubbing material, defects arising on the coating, etc. Because of these factors, the photo-orientation
method is being the most prospective method for the production of oriented layers for LC displays. The essence of the method is
the employment of spin-coated film of photochromic LC polymers deposited on a glass substrate and followed by irradiation with
polarized light. The light induces a uniaxial planar orientation of mesogen photochromic side groups (Figure 21).84 These
oriented polymer layers can be regarded as distinct ‘command’ surfaces, which orient the spread molecules of low-molecular-mass
liquid crystals, thereby determining the orientation of the LC director.
Azobenzene-containing polymethacrylates containing terminal cyanobenzene groups with spacers of various lengths and
possessing nematic and smectic phases with various temperature intervals of the LC phase were used as LC polymer command
surfaces20 (Figure 21).
CH3
CH2 C n=4 PAzo4M
COO n=6 PAzo6M
(CH2)n O N=N CN n=10 PAzo10M
All stages of the photo-orientational process are presented in Figure 21.

Polymer solutions are applied on glass plate (or other substrates) via the spin-coating method. Then, they are irradiated with
polarized light, which induces the orientation of mesogenic groups of the LC polymer. The LC cell is built from two glass pieces
with the orientational coating. Subsequent deposition of low-molecular-mass liquid crystals on this command surface causes their
orientation toward the long axis of the mesogenic groups. The introduction of small amounts of dichroic dyes (less than 0.5–
1.0 wt%) oriented in the same direction makes it possible to calculate induced dichroism D, which achieves large values
(DB0.70–0.72). These values are comparable with the same values of dichroism obtained by above-mentioned rubbing method.
However the photoalignment provides more homogeneous orientation without stretches and dust, if compare with rubbing
technique.
It is particularly remarkable that further irradiation with UV light and variation in the direction of light polarization causes the
reorientation of both the side groups of the polymers and the LC molecules.
Using the developed photo-orientation and reorientation processes in photochromic low-molecular-mass liquid crystals
authors84 demonstrated a possibility to use them for photopatterning.
The latent information recording, partially considered in the previous section, is one of the possible application of the above-
mentioned systems. Another example of the photopatterning for latent image recording is shown in Figure 22 for one of the
photochromic polymethacrylic series – PAzo4M, containing a spacer with (four methylenic groups) (see above).
Figure 22 shows the photos of the photopatterned cell prepared using PAzo4M as photoalignment coating filled with the
nematic mixture containing dichroic dye. A cell was first irradiated by polarized light with definite polarization direction. Then cell
was irradiation using the mask with polarized light having polarization rotated by 45 or 901 with respect to the initial polarization.
Image of letters ‘МГУ,’ which means the Russian abbreviation of ‘Moscow State University’ cannot be seen without a polarizer. The
image becomes visible when the polarizer is placed on the top of the cell. Thus, changing the position of the polarizer makes it
possible to obtain a negative or positive image. These photo-orientation polymer coatings (‘command’ surfaces) are profound
interest for applications in optoelectronics, photonics and display technology.
From the above it is well-established that the azobenzene-containing polymers can undergo a reversible E–Z (trans–cis)
photoisomerization process when excited with a polarized light, leading to a permanent molecular reorientation in a direction
perpendicular to polarization of the incident light. During this process, the polymer film follows the distribution of intensity or
polarization within the interference pattern and deforms, resulting in formation of surface relief grating (SRC). The mass transport
of polymer occurs macroscopically regular and periodic fashion across the polymer surface. The typical AFM image of SRC for
polymeric azobenzene containing films with a periodic molecular crientation is shown in Figure 23(a).85 This type of structure
corresponds to typical holographic grating recording using a single coherent light (532 nm) (monphotonic recording) that is the
Figure 22 Photos of the photopatterned cells on the base of photochromic command coating PAzo4M filled low-molecular-mass liquid crystals
with 0.1 wt% of dye. (Adapted from the paper Liquid crystals photoalignment by films of side-chain azobenzene-containing polymers with different
molecular structure. (Bobrovsky, A., Ryabchun, A., Shibaev, V.P. ) J. Photochem. & Photobiol. A:Chem. (2011) 218, 137–142, Figure6.84)
(a) (b)
Figure 23 (Adapted from the paper Biphotonic photochromic reaction results in an increase in the efficiency of the holographic recording process
in an azo polymer. (Sobolewska, A., Zawada, J., and Bartkiewicz S.) Langmuir (2014) 30, 17–21. Abstract.85)
basis of the majority of the applications polymers. The adjacent picture (Figure 23(b)) demonstrates biphotonic recording that
uses two light sources (532 and 405 nm) and characterized by significantly much more efficiency of the recording process.
However, the specific mechanism of SRG formation usually associated with mass migration remains incompletely understood.
Recently a group of scientists proposed a new mechanism of SRC formation in different asobenzene-containing polymer films
based on the polymer photo-photofluidization in the illuminated regions followed by the mass displacement from illuminated
to non-illuminated regions.86 These data were based on the use classical reological methods and the results of the amplitude
modulation-frequency modulation AFM, which permitted to suggest the mechanism for SRG formation based on athermal
photofluidization.86
However, regardless of a mechanism of SRG formation it is established that the light illumination of photosensitive LC film
exhibits a strong topographical response. This is very promising for applications in different fields, for example, in creation of micro-
and nanofabrication of complex periodic structures diffractive optical elements preparation of strain-sensitive diffraction gratings, etc.
Of particular interest is the wrinkling patterns in thin metal films generated from self-assembling LC polymers.87 Authors of this
work developed a new universal method that uses the photopatterning of LC polymer, which is accurately translated into a controlled,
intricately wrinkled metal surface. Remarkably, the patterns have an oscillation in amplitude of the wrinkles (Figure 24).
Photoalignment of polymerizable liquid crystals is followed by photopolymerization and sputter coating of a gold layer, which
induces compressive stress in the system. Heating the material above glass transition temperature releases stress through wrinkling;
the wrinkles form perpendicular to the alignment director of the LC polymer network due to the lower elastic modulus in that
direction (Figure 24). Many applications for wrinkled surfaces have been described: preparation of superhydro-phobic surfaces,
actuators, fabrication of patterned electrodes, optical focusing, etc.
6.3 Chiral-Photochromic LC Polymer Systems

The general concept of preparing such materials involves the synthesis of combined chiral-photochromic LC copolymers or
obtaining cholesteric mixtures based on nematic polymers and low-molecular-mass chiral and photochromic dopants.
Figure 25 shows the schematic representations of different variants of comb-shaped macromolecules containing mesogenic,
chiral, and photochromic groups, including combined monomeric units consisting of chiral and photochromic fragments.
Contrary to the photochromic LC polymers, the chiral-photochromic LC polymers offer a much wider opportunity for the creation
of photoactive and electrocontrollable materials and polymer films for color image recording.
Figure 26 schematically represents (a) light control over the helical structure of (b) a cholesteric photochromic polymer
through the use of a copolymer containing the combined chiral-photochromic group, and (c) a mixture of a nematic homo-
polymer with low-molecular-mass chiral-photochromic dopant.
Irradiation of the polymer film causes the photochemical E–Z isomerization of photochromic groups (e.g., azobenzene
fragments) (Figure 26(a)) which, being directly linked to the chiral fragment, change not only the configuration but also the shape
of the side groups (Figure 26(b)). This effect in turn causes a decline in twisting power β of the chiral fragment owing to a decrease
in its anisotropy (β2oβ1). In accordance with equation:
β ¼ dp1 =dxch at xch { 1 ½3
where xch is the molar fraction of chiral monomer units in the copolymer, adeclinein β leads to untwisting of the cholesteric helix
(P24 P1), which is accompanied by a shift in the peak of the SLR to the long-wave spectral region (Figure 26(b)). A similar result
Figure 24 General scheme of (a) wrinkle patterns preparation and (b) AFM image of the real winkled surface. (Adapted from the paper On-
demand wrinkling patterns in thin metal films generated from self-assembling liquid crystals. (de Haan, L.T., Leclère, P., Damman, P., Schenning,
A.P.H.J., Debije, M.G.) Adv. Funct. Mater. (2015) 25, 1360–1365. Figures 1(a) and 2(f)87).
1
3
2 3 1
Figure 25 Schematic representations of macromolecules of CL chiral-photochromic comb-shaped polymers containing (1) mesogenic, (2) chiral,
and (3) photochromic groups.
(a) (b) (c)

h
1
2 max
Figure 26 Photoinduced untwisting of: (a) the cholesteric helix in the films, (b) an LC copolymer containing chiral-photochromic monomer units,
and (c) a mixture of nematic homopolymer and chiral-photochromic dopant.
Figure 27 Schematic representation of (a,b) the diffraction grating recording in the cholesteric polymer with photo-tunable helical pitch. (c) Inset
– polarized optical microphotograph of observed texture. P1 and P2 are pitches of the helix (P24P1). (Adapted from the paper Stable selective
gratings in cholesteric LC polymer by photoinduced helix pitch modulation. (Ryabchun, A., Bobrovsky, A., Gritsai, Y., Sakhno, O., Shibaev, V.,
Stumpe, J.) ACS Appl. Mater. & Interfaces (2015) 7, 2554–2560, Figure 2.88)
(helix untwisting) arises from irradiation of the mixture of nematic polymers containing isomerizable chiral-photochromic dopant
(Figure 26(c)).
The combined LC copolymers and LC mixtures based on this concept are very promising materials for data optical recording
and storage. The UV irradiation of such polymeric films through a special pattern permits local optical properties to change and to
record a color image against the color background.
Figure 27 shows the scheme of the information recording on the planarly oriented LC polymer. Using the mask (or test
pattern), it is possible to change color locally and record the color image on the color film. This phenomenon opens up a new way
to record colored data and to store them on a colored background.
Depending upon the chemical structure of photochrome, this process can be irreversible or reversible; in the latter case, LC
polymer films display high fatigue resistance.
Another of the most interesting aspects of the same application principle is also associated with cholesteric LC polymers which
are used for creation of polarization and phase gratings. Cholesteric LC polymers containing chiral-photochromic fragments in
their monomer units or mixture nematic polymers with chiral-photochromic dopants can be used for optical data storage20,38
creation of the stable selective gratings by photoinduced helix pitch modulation.88 Such modulation is fabricated in the polymer
mixture (Figures 27(a) and 27(b)) by a nonpolarized UV irradiation with spatially modulated intensity that causes E–Z iso-
merization of a chiral-photochromic dopant decreasing its β-value in the irradiation zone of the LC cell (Figure 27 (b)). As a result
the untwisting of cholesteric helix takes place and its pitch (P2) increases. Such gratings are adjustable in the wide spectral range
(400–1000 nm) and can be visible in the form of alternate color strips on the optical microphotographs in polarized light as
shown in the inset of Figure 27(b).
This sophisticated method of the gratings fabrication has rather high diffraction efficiency and opens new possibilities for their
application in nanophotonics and optoelectronics.79–94
Introduction of two different photochromes in ternary copolymers (biphotochrome polymers) characterized by different
responses to light of a variable wavelength allows recording of optical information of two types on the same sample (so-called dual
dichroism) that opens very interesting possibilities for the creation of novel types of photopatterning color polymer thin films.35
6.4 Photo-Responsive LC Polymers as Photo-Optical Sensors

Cholesteric LC polymers (similar to the low-molecular-mass cholesterics) are appealing materials for use them as optical sensors,
due to their ability to form a one dimensional photonic supramolecular helical structure by self-assembly (see Section 6.1.2). LC
cholesteric polymers are usually obtained by copolymerization of nematogenic and chiral monomers or by introduction of chiral
dopants into the polymer-stabilized networks (Figure 19). As it was shown above cholesteric polymers exhibit a wavelength and
polarization SLR in the certain spectral range depending on chemical structure and concentration of the chiral fragments che-
mically or mechanically incorporated into the structure of polymers or networks. The length of this helical pitch can be influenced
by various external stimuli resulting in a change of the helical twisting power β (eqn [3]) and the selective reflection wavelength
(Figure 2).
This permits the use of the cholesteric LC polymers as optical sensors where changes can be observed with the naked eye or by
spectroscopic method. The ‘stimulus,’ i.e., the analyte can react with the chiral structure thereby changing its helical twisting power
β and therefore the reflection colour of the system. The reflection colour can also be changed by untwisting of twisting supra-
molecular helical structure due to interaction or absorption of the analyte with by the photonic polymer films (Figure 28).95
Using a similar approach authors of the article96,97 have developed a method of preparation of the photochromic-ionophoric
polymer-stabilized cholesteric networks containing crown-ether groups, which make it possible to form complexes with alkali- and
alkaline-earth metal ions.
Figure 29 shows a scheme of the cross-linked photochromic polymer film with the helical cholesteric supramolecular texture
containing crown-ether groups chemically linked with the network. It is seen that after exposure in an aqueous solution of metal
(potassium or barium) perchlorate salts the helical pitch P1 of the initial planar texture decreases and pitch P2 becomes less as P1
(P2oP1) due to the complex formation and shrinkage of the polymer network.
The values of maximum of SLR shift correspond to about 40–80 nm in dependence of the type of the analyte (Mn þ , ClO4).
Recently, a very interesting application of photochromic polymer cholesteric films for the detection of gaseous trimethylamine
(generated during putrefraction of fish products) was described by scientists from Holland who found the shift of SLR of the
cholesteric from the green region to the red region of the spectrum.98
Figure 28 Generalized scheme of the selective reflection band changes of cholesteric sensor to an analyte. Shrinkage of polymer sensor leads to
a blue shift, untwisting of cholesteric helix leads to the red shift band (P24P1). (Adapted from the paper Chiral nematic liquid crystals as one
dimensional photonic materials in optical sensors (Mulder, D.J., Schenning, A.P.H.J., Bastiaansen, C.W.M.J.) J. Mater. Chem. C (2014), 2, 6695–
6705. Figure 2.95)
Figure 29 Scheme of general working principle of polymer-stabilized photochromic LC network containing crown-ether moieties as a sensor on
metal ions. (Adapted from the paper A novel type of crown ether-containing metal ions optical sensors based on polymer-stabilized cholesteric
liquid crystalline films. (Stroganov, V., Ryabchun, A., Bobrovsky, A., Shibaev, V.) Macromol. Rapid Commun. (2012) 33, 1875–1881. Scheme 1.97)
Noteworthy, hydrogen-bridged, cholesteric LC polymers networks which are adopted as an optical sensor material to distin-
guish between ethanol and methanol. The discrimination between the alcohols is based on the diversity in molecular affinity of
ethanol and methanol with the hydrogen-bridged LC polymer network.99
These data demonstrate the possibility to prepare effective photochromic stimuli-sensitive cholesteric networks with a rapid
response of their optical properties to interaction with analytes.
Original method of application of chiral LC compositions for design of novel rotational sensors that are able to sense rotations
in a range between 0 and 51 with high accuracy as well as submicron displacements.100 The response of the system is related to the
inclination of the cholesteric helical structure. The spectral width Dlmax of the SLR is usually determined by optical anisotropy Dn
of cholesteric planes:
Dlmax ¼ DnP ½4
After the shear deformation induced by rotation of the sample the position of the maximum of SLR is changed and determined by
the equation
lnew ¼ nPnew cosðg0 g1 Þ ½5
where g1 is the angle between the axis of the cholesteric helix and substrate normal; Pnew is the helical pitch after deformation. The
method described allows for monitoring small rotational deformations on the order of tenth of angular minutes and its resolution
could be significantly enhanced by the employment of leverage.
6.5 Ionogenic LC Polymers as Self-Assembled and Phase-Microsegregated Liquid Crystals

LC polymers containing functional groups such as COOH, OH, NH2, and so on, along with mesogenic fragments, usually called
ionogenic LC polymers, are of special interest because of their highly pronounced hybrid structure and dual properties. The
occurrence of mesogenic fragments determining the development of self-assembled structures, in combination with functional or
charged groups, makes it possible to widen the opportunity for creating metal-containing LC polymers (ionomers) with 1D, 2D,
and 3D phase-segregated structures on various scales of length (1–1000 nm) formed by self-assembly of a variety of partially
incompatible molecular fragments.52,101,102 In the case of ionogenic systems (and especially ionomers), the tendency toward
formation of the smectic phase becomes more pronounced owing to specific intermolecular interactions such as hydrogen
bonding and ionic interactions. Such polymers are typical phase-segregated systems characterized by the sandwich structure, in
which layers are formed by nonpolar mesogenic groups and main polymer chains carrying charged carboxyl groups and metal ions
(in ionomers).
Figure 30 shows the molecular organization of LC ionomers in the smectic phase. It is seen that the packing of macromolecules
has the sandwich structure with alternation of layers formed by mesogenic groups and backbones carrying individual ions and so-
called multiplets composed of ion pairs. Such supramolecular structure can enhance anisotropic properties such as ionic con-
ductivity. In the smectic phases, the ion conductivities parallel to the smectic layer are sometimes 100 and more times higher than
those perpendicular to it.102 It is clear that wide opportunity for the molecular design of some complex systems built according to
the above-mentioned principle, as well as, polycomplexes in which positively or negatively charged macromolecules of poly-
electrolytes (e.g., poly(acrylic)acid) or their functionalized mesogenic copolymers served as a counterion, offer very wide
(b)
(a)
(с)
(d)
Figure 30 Structural model of the smectic LC ionomer: (a) multiplets; (b) individual ion-containing groups; (c) the region of aggregation of
mesogenic groups in the smectic layer (d is the layer thickness); and (d) the region of aggregation of polymer chains, ionogenic groups, and
multiplets in the interlayer spacing.
possibilities for the synthesis of new types of anisotropic materials, such as membranes with controlled permeability, conducting
LC polymers, and anisotropic LC gels.101–103
Composites obtained by mixing magnetic asymmetric nanoparticles with LC polymers open new pathways in the field of
creation of the magnetic filler inorganic particles oriented in polymer anisotropic matrices to improve the magnetic properties of
the composite materials.
6.6 LC Elastomers
The first publications relating to the synthesis of LC elastomers based on the cross-linked polysiloxanes containing mesogenic side
groups were produced by Finkelmann et al.56,57,104,105 The first phenomenological description of LC networks was presented by
Warner59 and later a comprehensive book concerning theory of LC elastomers was published.58 LC elastomer combines the
properties of a liquid crystal and an elastomer. It shows high molecular mobility combined with anisotropic order, which are
the characteristics of LC phase, and exhibits the rubber elasticity of a weakly cross-linked polymer network. The combination of
the two above-mentioned properties makes these materials very interesting for microengineering, where their integration can
induce the movement of a reduced volume engine. Temperature, voltage, and light are driving forces that can produce such
movements by inducing change of order in the LC structure. Small changes in the LC elastomer film cause strains of up to 150% in
a microdevice and the capacity to move up to 400 times its own mass due to the nematic–isotropic transition.103 In this sense, LC
elastomers are materials suitable for the application in microsystems technology for the creation of microactuator (such as pumps,
valves, switches, etc.) with potential uses in, for example, artificial muscles.
The majority of LC elastomers are based on the polysiloxanes or cyclic siloxane oligomers67 containing typical low-molecular-
mass liquid crystals chemically linked to the polysiloxane backbone. One of the remarkable features of LC elastomers having
nematic structure is an LC monodomain structure – the LC analog of a single crystal. Such structures are formed when an external
mechanical field is applied to a nematic elastomer. In this case, the polydomain structure with isotropic director distribution is
transformed into the monodomain state in which all mesogenic groups are arranged parallel to each other with an ideal uniform
director orientation. Such nematic elastomers can be considered to be suitable new materials for optical applications (contact
lenses) nonlinear optics, and could be applied as piezoelectric sensors and ferroelectrics.
LC elastomers based on the side-chain and main-chain LC polymers containing rather small concentrations of the chiral
mesogens can form SmC mesophase-possessing domains with permanent electric dipole moment, which exhibit piezoelectric
properties.106,107 The application of an uniaxial mechanical field (shear) produces a centrosymmetric morphology, where the
piezoelectric effects are observed. The piezoelectric coefficient reaches its maximum at a certain shear angle that corresponds to the
completion of polydomain to monodomain transformation. The piezoelectric module of different types of such LC elastomers can
be higher than those of commercial piezoelectrics, such as lead zirconate titanate, or poled polymers such as poly(vinilidene
Figure 31 Photomechanical response of a LC polymer sample doped with azo-dye. (Adapted from the paper Photomobile polymer materials:
from nano to macro. (Ikeda, T., Ube, T.) Mater.Today (2011) 14, 480–487, Figure 3(a).108)
fluoride). As is shown in Reference 107 such SmC LC elastomers can be used as soft electromechanical actuators for frequencies
below the kilohertz range, at temperatures ranging from the glass transition up to the smectic to isotropic transition.
6.7 Photomechanical LC Actuators

Apart from electromechanical actuators mentioned in the previous section, LC polymers turned out to be very effective for creation
of the miniature micromechanical smart materials capable of changing their macroscopic properties under the influence of the
light irradiation. The most common LC polymers, which are in use for such purpose are comb-shaped LC polymers and their cross-
linked analogous containing photochromic fragments in particular azobenzene dyes.108–111
The main principle of azobenzene-containing photo-actuators is based on the photoinduced phase transition from a LC to an
isotropic state that leads to the change in the geometric dimensions of the polymer sample. In turn the photoinduced iso-
tropization is associated with transformation of ridged mesogenic rod-like molecules (E-azo-containing isomers) to the Z-isomers
having a bent-like shape, which are formed during the light driven photoisomerization process.108,109 As a result the photoinduced
bending deformation of the azobenzene-containing samples is observed. Figure 31 shows a large bending angle for a sample of a
cross-linked LC polymer film doped with an azo-dye under 80 ms illumination by Ar þ laser.108
Several types of oriented LC polymer systems have been used for actuator creation. Among them there are polymer systems
with monodomain planar or homotropic alignment, polymer with twist and splay-bend molecular organization or polydomain
(non-oriented) structure. The vast majority of polymer actuators described in the literature are based on cross-linked LC sys-
tems.109–111
The unusual 3D shape-control and actuation, usually inherent to biological systems, was realized for chiral LC polymer
networks prepared with a range of cross-link densities.110 The 3D shape of these materials based on the cross-linked polyacrylic
copolymers is strongly dictated by both cross-link density as well as the preparation conditions (polymerization temperature). All
of these materials undergo torsional inversion of the handedness with increasing temperature. The temperature at which the
material flattens (crossover between handedness inversion) can be positioned by the polymerization temperature. Monoliths
prepared with either multimaterial composition or multi-director orientation are shown to exhibit spatial variation in shape
adaptivity. The thermomechanical deformation of one of the obtained polymer sample can traverse from coiled at room tem-
perature through a flat state before inverting handedbess (Figure 32). The two comprehensive reviews relating to the design,
synthesis and operation of spring-like materials capable of converting light energy into mechanical work at the macroscopic scale
and creation of polymeric shape memory materials are presented in the refs. 111 and 112.
Another approach is described in the article.113 This method is developed on the base of combination of properties of a
stretched polyethylene porous films (host matrix) and cross-linked azobenzene-containing LC polymer network formed directly
inside of the PE matrix pores. A stretched porous structure of PE films possesses a very strong alignment property with respect to
liquid crystals. Mixture of mono- and bifunctional photopolymerizable acrylates together with azobenzene-containing diacrylates
are good oriented by the oriented walles of the poreses which can be considered as specific ‘microcontainers.’ This mixture is
polymerized under heating forming continual cross-linked structure in the PE porous stretched film.
The bending deformation is caused by the UV-illumination of the film followed by E–Z isomerization of the azobenzene
fragments of LC polymer network. The isomerization process occurs mainly at the top surface of the film due to high absorption
coefficient of azobenzene groups prevented further penetration of light through the film thickness. This phenomenon, coupled
with a uniaxial orientation of azobenzene fragments leads to deformation of the film toward the light as schematically
shown in Figure 33.113 The reverse process (unbending process) is a result of the back process of Z–E isomerization (Figures 33(a)
and 33(b)).
These kinds of photo-actuators combine several advantages such as high deformation and their complete reversibility, lack or
need for alignment coatings and cell preparation, good mechanical properties, and relatively low cost.
Figure 32 Thermally-initiated torsional (out-of-plane) responses of LC cross-linked polymer stripe. (Adapted from the paper Twists and turns in
glassy, liquid crystalline polymer networks. (Wie, J.J., Lee, K.M., Ware, T.H., White T.J.) Macromolecules (2015) 48, 1087 1092, Abstract.110)
Figure 33 (a) Scheme of the reversible bending of the LC-PE film (LC composite) actuator. The green fragment corresponds to the azobenzene
groups and the blue one is the non-photochromic group. (b) Bending deformation of a PE composite thin strip under UV irradiation as a function
of time. (Adapted from the paper Novel generation of liquid crystalline photo-actuators based on stretched porous polyethylene films. (Ryabchun,
A., Bobrovsky, A., Stumpe, J., Shibaev, V.) Macromolecular Rapid Communications (2012) 33, 991–997. Figure 2.113)
7 LC Block-Copolymers
Among the above-mentioned LC homo- and copolymers, LC block-copolymers, consisting of the amorphous and LC subblocks, as
well as double and triple LC subbblocks with the different mesophase structures attract the special attention of the researches
(Figure 34).114–120
Polymers composed as a rule of two blocks with amorphous and LC structure are dominant among LC block-copolymers.
These polymer systems are usually characterized by micro phase-segregated structures, in which LC mesogenic subblocks form
cylinder domains incorporated into the matrix (Figure 35).114
The triblock-copolymers containing LC or crystalline subblocks open up new possibilities to create a number of unusual
combinations of hierarchical supramolecular structures in the polymer films of nanometer dimensions. Figure 36(a) demonstrates
molecular constitution of triblock copolymer consisting of one semicrystalline poly(ethylene oxide) central subblock (PEO)
surrounded by two LC terminal polymethacrylate blocks bearing side-chain cholesterol mesogens (Chol), prepared by reversible
addition-fragmentation chain transfer (RAFT) polymerization (Figure 36).115
By varying the LC content in the triblock copolymers, different hierarchical structures including ‘LC lamellar in PEO lamellae’
and ‘PEO cylinders in LC matrix’ can be obtained (Figures 37(a) and 37(b)). Such the microsegregated LC domains can efficiently
Figure 34 Schematic representation of the molecular structure of double block-copolymer consisting of a amorpous and LC subblocks.
b PS-b-PAz
140
76
O O (CH2)10 O N
N (CH2)4 CH3
Figure 35 (a) Microphoto of image of double block-copolymer consisting of polystyrene (PS) and mesogenic photochromic methacrylate (PAz)
subblock and (b) schematic representation of its ‘supramolecular’ domain structure. (Adapted from the paper New strategies and implications for
the photoalignment of liquid crystalline polymers. (Seki, T.) Polymer Journal (2014) 46, 751–768, Figure 11.114)
Figure 36 Molecular structure of triblock copolymer consisting of linear poly(ethylene oxide) (PEO) and mesogenic cholesteryl comb-shaped
fragments. (Adapted from the paper Tailoring crystallization behavior of PEO-based liquid crystalline block copolymers through variation in liquid
crystalline content. (Zhou, Y., Ahn, S.-k., Lakhman, R.K., et al.) Macromolecules (2011) 44, 3924–3934, Abstract.115)
Figure 37 Schematic illustration of the hierarchical structures of triblck-colopymer (see Figure 36): (a) LC lamellar in PEO lamellar and (b) PEO
cylinders in LC matrix. (Adapted from the paper Tailoring crystallization behavior of PEO-based liquid crystalline block copolymers through
variation in liquid crystalline content. (Zhou, Y., Ahn, S.-k., Lakhman, R.K., et al.) Macromolecules (2011) 44, 3924–3934, Figure 4, 5.115)
Figure 38 Schematic molecular structure of two types of triblock copolymers.
confine the crystallization; these block-copolymers provide a practical method of exploiting hierarachiral structures to regulate the
supramolecular organization and physical properties of nanodimensional triblok-copolymers.
The fully LC triblock-copolymers consisting of nematogenic and photochromic subblocks with their different distribution
along their macromolecules119 (Figure 38) obtained and their photochromic and photo-orientation processes under light illu-
mination were studied.
The photochromic and chiral-photochromic block-copolymers possessing the photo-responsive properties such as photo-
induced orientation, SRG formation, optical nonlinearly, photomechanical thin-film contraction, and bending, and many other
features are attracting most recent attention for their unique architecture and fascinating supramolecular structure.116–120
8 LC Dendrimers with Mesogenic Groups
Among the wide variety of main-chain and side-chain LC polymers, the superbranched polymers with dendritic structures fill a
highly important place in the field of low-molecular-mass and macromolecular compounds. Synthesis and investigation of
dendrimers stimulated the interest of researchers to the creation of LC systems combining the spherical shape of the molecules
with an anisotropy of the rigid rods. Actually, the incorporation of mesogens into a dendritic (ball-shaped) architecture is an
intriguing design approach, which results in the fabrication of hybrid structures combining the LC properties and dendritic
functionalities and shapes.
These studies led to the discovery of a new class of liquid crystals whose molecules contain the dendritic matrix chemically
bonded to mesogenic fragments situated both inside the hyperbranched structure and as terminal groups of the dendritic core
(Figure 39).
(a) (b)
(c) (d)
Figure 39 Schematic structures of several types of LC dendrimers with different arrangement of mesogenic groups. (a) Mesogenic groups are in
the whole volume of a molecule. (b) Molecule of LC dendrimer with terminal mesogenic groups, Homodendrimer. (c) Stat-codendrimer. (d) Block-
codendrimer. 1 – Matrix (core) of dendrimer; 2 – spacer; 3 – mesogenic group.
Most studies are devoted to the latter type of LC dendrimers containing terminal mesogenic groups. In this case, the same
principle of autonomy of mesogenic groups is valid similar to the ‘spacer concept’ used for obtaining LC comb-shaped polymers.
This principle implies the chemical bonding of mesogenic groups to the dendritic matrix via aliphatic spacer.
At present, several hundred LC dendrimers including homodendrimers and statistical and block-codendrimers have been
synthesized; their structure may be represented as a combination of three basic structural elements: polymer matrix, or core, spacer,
and mesogenic fragments located at the periphery of spherical dendritic molecules (Figure 39).121–124
Poly(propyleneimine), poly(amidoamine), siloxane, carbosilane, and other derivatives are most often used as initial polymer
matrices. Spacers are usually aliphatic chains of various lengths, and mesogenic fragments cover the whole arsenal of classical low-
molecular-mass liquid crystals.
The main feature of LC dendrimers is their dual nature combining the superbranched matrix (core) and rigid-rod mesogens
which, as a rule, are incompatible to each other. The formation of LC mesophases is the result of microsegregation processes
between the terminal mesogens and the internal (e.g., siloxane or carbosilane) matrices. For the low generations of the LC
dendrimers, this process leads to the layer (smectic) packing of mesogens, and for the high (fourth–fifth) generations the columnar
phases are formed. Structural models of dendrimer packing are presented in refs. 121–124.
9 Liquid Crystals Dispersed in Polymers and LC Composites
It this section we will very briefly consider some aspects of researches relating to the complex LC polymer systems including
polymer-dispersed liquid crystals (PDLCs), ‘polymer network liquid crystals,’ encapsulated polymer films, and LC composites with
quantum dots (QDs).
9.1 PDLCs
PDLCs, polymer network (cross-linked) LC systems, and encapsulated liquid crystals in polymer matrix are the subject of a great
number of publications and patents.14,21,125–129 PDLCs are prepared from mixtures of low-molecular-mass nematic liquid crystals
which in the form of microdroplets (0.5–1 mm) are dispersed in polymer films, such as poly(vinyl alcohol), poly(vinyl acetate),
and acrylic copolymers. Such compounds are usually used as sandwich cells, or polymer compositions with liquid crystals (or
mixtures of reactive monomers with liquid crystals followed by their polymerizations) which are placed between conducting
glasses or polymer films (Figure 40). An important feature of such cells is the proper selection of refractive indices of a matrix
(polymer) (np) and a mixture of liquid crystals (no) so that the initial nontransparent mixture becomes optically transparent under
application of an electric field. Figures 40(a) and 40(b) shows an electro-optical electroconducting cell containing liquid crystal
droplets in polymer matrix before and after switching on an electric field and Figure 40(c) an transmittance of the cell as a
function of applied voltage.
The advantages of such systems for use in practice are evident. They do not need the presence of polarizers (this is very
important for miniaturization of optical devices) and successfully combine the properties of polymers (with their ability to form
flexible films and coatings), as well as the unique properties of liquid crystals capable of orientation during the action of weak
electric field. Under the electric field action PDLC cells change in optical characteristics (transparence, birefringence, light scat-
tering, etc.). The characteristic value of the controlling voltage usually lies within the interval 20–80 V, and a response time may
reach 1 ms or less.
Recent trends are toward increased production and application of PDLC deices under the names smart glasses or switchable
glasses, which also called smart windows or switchable windows. Most of the smart PDLC windows are used today in the form of
the self-adhesive laminate films for interior and exterior settings for privacy control (e.g., conference rooms, intensive-care-areas,
bathroom/shower doors) as a temporary projection screen. One example of using the smart switchable interior panels is shown in
Figure 41.
9.2 Cross-linked LC Polymer Systems

A new version of LC polymer composites is a low-molecular-mass nematic or cholesteric liquid crystals stabilized by polymer
networks (so-called ‘polymer network liquid crystals’). Such materials are blend compositions that are prepared as a rule via the
photopolymerization of bifunctional mesogenic monomers (including LC monomers) in liquid crystals. These systems contain
70–90% of liquid crystals and are characterized by a low degree of cross-linking forming LC gels. Gel structure can be easily
regulated under the action of an electric field. Such LC systems are used for the creation of devices with electrocontrollable light
scattering and transparency. The advantages of these systems are low enough control voltages (as low as several volts) and a much
faster response time when compared with PDLCs.128,129
The areas of application of PDLC films may be very wide: electrically controlled blinds, fast-acting optical attenuators, large-
sized display boards, for example, traffic control signs, petrol pump indicators, railway station, and airport information boards,
and so on.
Figure 40 Electro-optical switching in PDLC films: (a) and (b) ‘off’ and ‘on’ states, respectively. (c) Transmission of PDLC cell as a function of
the applied voltage.
Figure 41 The interior smart panels before (off) and after switching on.
9.3 Encapsulated Polymeric Films

The next group of LC composites – encapsulated polymeric films are usually based on the cholesteric liquid crystals by encap-
sulating them in a polymer and using printing technologies to apply them to the supporting substrate.130 The preferred fabrication
method involves producing the LC droplets with the cholesteric liquid crystals mixture. The LC droplets can be microencapsulated
with gelatin shell or they are dispersed in a continuous polymer matrix. In current use, laminating the liquid crystal mixture
between two embossed plastic sheets is widely exploited. The cholesteric polymer films obtained by all these methods are widely
Figure 42 Thermograph of a human hand. The red colour corresponds to about 30 1C, the blue color – 32–33 1C.
used for temperature-sensing applications. Figure 42 shows thermograph of a human hand. The red colour corresponds to about
30 1C, the blue color – 32–331C.
Such thermochromic materials are commercially available and offer color plays between 0.5 and 51 over the temperature range
from 30 to þ 110 1C for indicating temperature in the home and office, for medical thermography producing visual thermal
maps of a series of deceases – breast cancer detection, vascular disorders, san grafting, and so on. In addition, thermal mapping of
inanimate objects (detection of structural flaws, hot spots in electrical circuits indicating shorts, and heat transfer effects in
aerodynamic models) can also be useful. Using the cholesteric materials, a number of fashion ideas have also been explored
including slogans on fabrics and ‘mood’-indicating jewelry.
9.4 LC Composites with QDs

Organic–inorganic hybrid materials, in particular LC compounds doped with nanoparticles, QDs attract a great attention due to
their unique optical properties, switchability, and the variety photonics.131–139
Despite a great progress in the field of the QD-LC-composites the introduction of a large concentration of QDs into liquid
crystal media is still a challenging task. Usually the authors of the publications offer an general approach based on the surface
modification of QDs (such as CdSe/ZnS) with complex mesogen-containing ligands, which resulted in the preparation of ther-
modynamically stable QDs solutions in LC matrix. However, in the most cases the concentration of QDs does not exceed 0.10–
0.25% and they cannot exhibit their remarkable photoemission properties.
Figure 43 demonstrate the realization of the above-mentioned general approach on the two specific examples.20 Figure 43
shows how the CdSe/ZnS QDs containing trioctylphosphine oxide as ‘edging’ may be modified via interactions with mesogenic
compounds and the terminal sulfhydryl groups.20,138
Schematic representation of a model proposed for the organization of the mesogen-containing ‘hybridic nanoparticles’ within
the LC polymers is shown in Figure 44.
The introduction of these modified QDs into low-molecular-mass liquid crystals136 and LC polymers 20,138 (under the con-
dition of a similar chemical structure of the mesogenic groups) must lead to the generation of mutually soluble systems with
homogeneous structures.
In addition to LC polymers, QDs modified with mesogenic or other asymmetric groups can be introduced into oriented porous
materials, where they are arranged along the walls of macro- and micropores. The porous polyethylene films were used to introduce
QDs based on CdSe/ZnS with the application of aliphatic alkenes.137 The obtained polymer samples are elastic films, whose contents
of QDs may be varied within the limits of 15%. UV irradiation of the films results in bright fluorescence (Figure 45).
10 Miscellaneous LC Polymers
Another type of LC polymers without mesogenic groups (usually referred to as ‘mesomorphic’ polymers) involves organic and
organoelement polymers, including poly(organophosphazenes), poly(organosiloxanes), polysilanes, and even some polyolefins.
Figure 43 Schematic representation of modification of QDs (CdSe) by mesogen-containing compound. (Redrawn from the paper Liquid-
Crystalline Polymer Systems: From the Past to the Present. (Shibaev, V.P.) Polym. Sci. Ser. A (2014) 56, 727–762. figure on p.758.20)
Figure 44 Possible arrangement of modified hybridic QDs in the matrix of comb-shaped LC polymers. (Redrawn from the paper Liquid-
Crystalline Polymer Systems: From the Past to the Present. (Shibaev, V.P.) Polymer Science ser. A (2014) 56, 727–762. figure on p.759.20)
These polymers are able to exist in a state which is neither truly crystalline nor describable in the framework of an LC state.
The term mesomorphic is more appropriate for these systems, as well as for other systems such as block copolymers, graphitizable
cokes, and some cellulose derivatives. The mesophase state for the above-mentioned flexible polymers is the rule rather than the
exception. The experimental and theoretical studies of such polymers, usually referred to as conformationally disordered crystals
(condis crystals), are primarily directed toward the development of the so-called structural rheology of polymer systems.140–144 We
can imagine that in reality the range of such polymers is much wider. The term mesomorphic, wider in meaning than the term ‘LC,’
is probable quite pertinent for the description of any system with some type of structure intermediate between the crystalline and
Figure 45 Fluorescence spectrum of PE-QDs-composite film (a) and the same film after excitation by light 365 nm. (Redrawn from
the paper Polyethylene-based composites containing high concentration of quantum dots. (Bobrovsky, A., Shibaev, V., Elyashevitch, G.,
et al., 2015. Polyethylene-based composites containing high concentration of quantum dots. Colloid Polym. Sci. 293, 1545–1551.
Figure 4 and 5.137)
isotropic ones. All these terminological questions relating to low-molecular-mass liquid crystals and LC polymers are compre-
hensively considered in the IUPAC document on Nomenclature of LC compounds.28
11 Conclusion
Liquid crystals, both low-molecular-mass and polymeric materials, remain as fascinating hybrid materials and their useful physical
properties will be widely used in many applications. The LC polymer family embraces the main-chain, side-chain, and cross-linked
(i.e., network or elastomer) polymers of nematic, smectic, and cholesteric mesophases types. LC dendrimers and LC ionogenic
copolymers, LC ionomers and LC polymers, ionophoric compounds, LC compounds, and LC gels are a rather novel generation of
very unusual and interesting LC compounds.14,20,38,144
The present time is characterized by the rapid development of studies aimed at the construction of nanostructured materials
with external-stimuli-controlled physicochemical properties.144–147 In this respect, the multifunctional comb-shaped LC polymers
offer a vivid example of self-organized thermocontrolled, photocontrolled, and electrically controlled nanostructured materials
(field-responsive smart materials) that show promise for various applications: optics, optoelectronics, photonics, display tech-
nology, optical memory devices, telecommunications systems, and so on.
Wide possibilities are open owing to the use of photochromic LC polymers in photonics: for preparation of coatings
self-orienting under the action of light (display technologies),73,75 laser media based on polymer cholesterics,148,149 command
surfaces providing orientation of low-molecular-mass liquid crystals,38 and molecular motors and other photocontrollable
supramolecular structures.149 Moreover, photosensitive polymers that reversibly change their optical properties are a means
of obtaining photocontrollable reversible systems, light-sensitive sensors, and sensor devices: promising candidates for
various applications. In this field, azobenzene-containing polymer systems are of special interest, as azobenzene has been
shown to change its configuration instantly but reversibly by illumination with UV and visible light, respectively, without
generating and side products. Thus, azobenzene-containing polymers are used in supramolecular assembly, in covalent functio-
nalization of different polymer and metal surfaces, or for the switching of bioactivity of some biomacromolecules.150 All these
directions are directly associated with the progress of studies in the fields of photonics and telecommunications and information
technology.
There is no question that recently initiated research into the synthesis of LC polymers linked to nanoparticles has opened a new
path in the study of such hybrid LC systems.151–155
Considerable attention of researchers is paid to the synthesis and characterization of LC elastomers and LC gels employed as
actuators and for the manufacture of robots and various biomimetic systems, which mechanically operate owing to a change in
their supramolecular structure under illumination. Among these studies, experiments on light-induced displacement of polymer
LC samples that were performed, for the first time, under the guidance of Ikeda are worth mentioning.156–159 The comprehensive
reviews relating to recent advances and challenges in the development and applications of stimuli-responsive and semiconducting
polymer materials, as well as cross-linked LC systems that are self-assembled from nanostructured building blocks are given in
ref. 38 (Box 2).
Box 2
Although the science of the LC polymers is not fully mature, it has attracted significant research interest and has already made
tremendous progress. As investments and human resources continue, the LC polymers are expected to have an even brighter
future. (Wang and Zhou, 2004).
Acknowledgment
Author (Valery Shibaev) is very grateful to the Russian Science Foundation (grant 14-13-00379) for financial support.
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Liquid Crystalline Polymers

Chapter · December 2016

Valery Petrovich Shibaev

Nonlinear optical effects in dye-doped liquid-crystalline polymers View project

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Liquid Crystalline Polymers$

Reference Module in Materials Science and Materials Engineering doi:10.1016/B978-0-12-803581-8.01301-1 1

1.1 Historical Overview

2 Constitution and Structure of Low-Molecular-Mass Liquid Crystals

CH3 CH3 CH3

Crystalline LC state Isotropic

120 130 140 150 160 170 180 190 200

Table 1 Some low-molecular-mass liquid crystals forming different LC phases

No Compounds and its structural form Types of liquid crystals and

3 CH3 CH3 CH3 Cr 71 Sm 79 Ch 85 I

CH3 (CH2)12 COO

Table 2 Main types of variously shaped molecules forming general LC phases

Box 1 Examples of typical mesogenic groups

(a) (b) (c)

3 LC Polymers: General Consideration

(a) (b) (c) (d)

Figure 5 Different types of molecular architectures in LC polymers.

4.1 Thermotropic LC Polymers

Aliphatic side groups (CH2)n CH3 , n= 3-15

HO C COO (CH2)2 OOC O H

4.2 Lyotropic LC Polymers

Table 3 Basic structural fragments of lyotropic poly(aromatic amide)s

Aromatic diacid Aromatic diamine

HOOC COOH H 2N NH2

HOOC COOH H 2N NH2

HOOC N=N COOH H 2N N=N NH2

4.3 Properties and Application of LC Main-Chain Polymers

Index Kevlar-49 (USA) Arenka (Tvaron) (Holland) Terlon (USSR)

Figure 9 Schematic molecular structure of a side-chain (comb-shaped) polymer.

5.1 Principles of Synthesis

Me = Li, Na, Rb, Cu, Co, Ni

Figure 12 Schemes of (a) covalently-bonded and (b) hydrogen-bonded LC polymer networks.

5.2 Structural Features of Side-Chain LC Polymers

(a) (b) (c)

Nematic structure Smectic structure

Cholesteric (chiral nematic) helical structure

Frozen oriented Tg LC phase T iso Isotropic

5.2.1 Polymer backbone

5.2.2 Spacer length

5.2.3 Mesogenic group structure

5.2.4 Molecular dynamics

6 Properties and Application of Side-Chain LC Polymers

6.1 LC Polymers for Passive and Electrically Controllable Optical Elements

6.1.1 Nematic LC polymers

6.1.2 Cholesteric LC polymers

CH2=CH CH2 CH CH2 CH

6.2 Photochromic LC Polymers

P∞ cos 2 α > 0, Δn = 0 P∞ cos 2 α > 0, Δn ~ 0.2 − 0.3

All stages of the photo-orientational process are presented in Figure 21.

6.3 Chiral-Photochromic LC Polymer Systems

β ¼ dp1 =dxch at xch { 1 ½3

(a) (b) (c)

6.4 Photo-Responsive LC Polymers as Photo-Optical Sensors