Accepted Manuscript

High performance liquid crystalline physical gels prepared by side chain liquid
crystalline polymers

Jianhang Zhao, Yongjie Yuan, Lei Chen, Ye Li, Hailiang Zhang

PII: S0032-3861(18)30321-5
DOI: 10.1016/j.polymer.2018.04.027
Reference: JPOL 20507

To appear in: Polymer

Received Date: 23 December 2017

Revised Date: 5 March 2018
Accepted Date: 8 April 2018

Please cite this article as: Zhao J, Yuan Y, Chen L, Li Y, Zhang H, High performance liquid crystalline
physical gels prepared by side chain liquid crystalline polymers, Polymer (2018), doi: 10.1016/
j.polymer.2018.04.027.

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High performance liquid crystalline physical gels prepared by side

chain liquid crystalline polymers

Jianhang Zhao, Yongjie Yuan, Lei Chen, Ye Li, Hailiang Zhang*

Key Laboratory of Polymeric Materials and Application Technology of Hunan

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Province, Key Laboratory of Advanced Functional Polymer Materials of Colleges and
Universities of Hunan Province, College of Chemistry, Xiangtan University, Xiangtan
411105, Hunan Province, China.

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Abstract

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Liquid crystalline physical gels (LCPGs) with stable mechanical properties and fast
electro-optical response properties were prepared through the self-assembly of side

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chain liquid crystalline polymers (SCLCPs) with different spacer length poly
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[ω-4'-cyano-(1, 1'-biphenyl)] acrylate (PmACB, m is the spacer length of
SCLCP, m=0, 2, 4) as gelators in a nematic liquid crystal, 4-pentyl-4'-cyanobiphenyl
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(5CB). The gel-sol phase transition temperature (TGS), micro morphology, mechanical
properties and electro-optical properties of LCPGs (SCLCPs/5CB) were
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systematically studied. The results show that only P0ACB can form stable liquid
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crystalline physical gels in 5CB and show excellent thermal stability, good
self-supporting ability and fast electro-optical response properties. The TGS of 6wt%
P0ACB/5CB gel is 192℃, and it also showed stable mechanical properties, its
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storage modulus is about 1.0×104 Pa. The threshold voltage (Vth) and saturation
voltage (Vsat) of P0ACB/5CB gel with 3wt% concentration are 0.29 V µm-1and 3.906
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V µm-1 respectively, and the off state response time is only 6.748ms. Moreover, the
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addition of the polymer does not affect the electro-optical response of the LCPGs.

Key words: Liquid crystalline physical gels, side chain liquid crystalline

polymers, electro-optical properties, optoelectronic materials

Introduction
Liquid crystal is a kind of functional soft materials which possess both ordered
structure of crystal and fluidity of liquid [1-4]. According to the order of liquid
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crystalline phase, it can be divided into nematic [5], smectic [6] and cholesteric liquid
crystal [7]. Among them, the nematic liquid crystal possesses best fluidity because of
the completely disordered state of its molecular centroid, and can make quick
response to external field. When the electric field is applied，the alignment of nematic
liquid crystal molecules will change, which leads to the change of optical properties of

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liquid crystals. Thus, nematic liquid crystals, such as 5CB, are widely used as display
materials [8-11].

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The fluidity of the nematic liquid crystals endows its sensitive response to the
external field, but it also loses mechanical stability. As a result, liquid crystals are

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usually injected into liquid crystal cells when used as liquid crystal displays (LCDs).
In recent years, research study found that introducing gelators into nematic liquid

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crystal to form stable LCPGs is another effective way to prepare LCDs [12-14].
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LCPGs is a novel class of stimuli responsive and thermally reversible soft solid
materials which comprise a three-dimensional fiber network formed by self-assembly
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of gelator via non-covalent interactions in liquid crystals [15] .Compared with the
traditional LCDs, LCPGs abandon the use of liquid crystal cells, which greatly
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simplified the LCDs structure, and the preparation process has been greatly simplified.
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Meanwhile, the electro-optical response properties of liquid crystals are not affected
by the addition of gelators, on the contrary, the oriented gelator fiber network is
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beneficial to improve the electro-optical response speed and contrast ratio [16].
Compared with the traditional polymer dispersed liquid crystals (PDLCs), LCPGs
also have lots of incomparable advantages, such as thermoreversibility, very low
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dosage of gelators and easy synthesis.

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LCPGs mainly consist of two components: one is the three-dimensional fiber

networks form by the gelator, another one is the working substance, such as 5CB. The
properties of LCPGs are closely related to the chemical structure of gelators, and
therefore the selection of gelator is critical to obtain high performance LCPGs.
According to the relevant research, gelators used for LCPGs can be divided into two
major categories: low-molecular weight gelators (LMWGs), and polymer gelators.
LMWGs have many advantages, such as easy preparation, large variety of gelators
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and low dosage. A large number of LMWGs such as amides [17-18], amino acids and
their derivatives [19-22], urea compounds [23], cholesterol compounds [24-25],
phenanthrene and its derivatives [26], sorbitol and their derivatives [27] have been
designed and synthesized to gelling liquid crystal since Kato et al. [28] first reported
LCPGs using LMWGs gelling room-temperature nematic LCs early in 1998. Xie et al

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[27] reported a LCPGs with high modulus based on LMWGs
1,3:2,4-di-O-benzylidene-D-sorbitol (DBS),

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1,3:2,4-di-O-p-methylbenzylidene-D-sorbitol (MDBS) and
1,3:2,4-di-O-m,p-dimethylbenzylidene-D-sorbitol (DMDBS). Its storage moduli were

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able to exceed 104 Pa when the gelator content is increased to 1.5 wt%. However, the
saturation voltage (Vsat) and off state response time (τoff) were greatly increased

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compared with 5CB. Chen et al. [29] reported stretchable light scattering display
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based on LCPGs with poss based dendrimer as gelator. Meanwhile, the transparency
of LCPGs can be controlled by UV irradiation time. It is regrettable that author did
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not characterize the electro-optical response performance. Polymer is also a common

gelator used for LCPGs. Triblock copolymers [30], polymer particles [31] and
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SCLCPs [32] are usually used to prepare LCPGs. Kornfield et al. [30] used triblock
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copolymers as gelator to prepare LCPGs. However, the synthetic method of triblock

copolymers was complex and the storage moduli of triblock copolymers/5CB LCPG
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is not high enough. Wood et al. [31] reported a LCPG based on PMMA particle. Its
storage moduli were able to exceed 104 Pa, however, the volume fraction of PMMA
particle must be greater than 50%. Alexey Bobrovsky et al. [32] for the first time
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prepared photochromic LCPG using SCLCPs containing azobenzene group as gelator.

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However, the relationship between the structure of SCLCPs and the properties of
LCPGs has not been studied. Based on the above analysis, we can find that the
preparation of high performance LCPGs is still a big challenge.
In recent years, our team found that side chain liquid crystal polymers can form
stable physical gel in organic solvent via π-π interaction and main chain
entanglements with low additions (lower than 1wt%). We prepared a series of
polymer organic gels with excellent thermal stability, good self-supporting ability and
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low additions by introducing side-chain liquid crystal polymers into common organic
solvents, such as n-heptane, triethylamine and so on [33]. We also prepared a series of
form-stable phase change materials (FSPCMs) with high enthalpy of phase change,
excellent thermal stability and high modulus by adding side-chain liquid crystal
polymers into paraffin, and the properties of FSPCMs can be controlled by

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modification of the chemical structure of side chain liquid crystalline polymers, such
as backbone structure, length of terminal groups and flexible spacer [34-35]. Based on

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the above results, we assumed that the high performance LCPGs with excellent
thermal stability, high modulus and excellent electro-optical response performance

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could be obtained by introducing SCLCPs with different chemical structures into
5CB.

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In this paper, we reported a series of SCLCPs as new type gelators for 5CB. The
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molecular structure and synthesis routes of SCLCPs PmACB with different spacer
length were shown in Scheme 1. The gelation abilities of PmACB were studied by
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“tube-testing method”. The properties of LCPGs including thermal stability,

mechanical properties and electro-optical properties were also systematically studied
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and detailed investigation into the relationship between the performances of LCPGs
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and the chemical structures of SCLCPs were made.

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Scheme 1 synthesis routes of monomers and polymers; (a) synthesis of
monomers and polymers without flexible spacer; (b) synthesis of flexible spacer
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monomer and polymers

Experimental
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Materials
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4-pentyl-4'-cyanobiphenyl (5CB) was purchased from Yantai Derun liquid crystal

material Co. Ltd. 2, 2′-azobisisobutyronitrile (AIBN) was recrystallised from
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methanol. Anhydrous tetrahydrofuran (THF) was distilled from sodium and

used immediately. 4-(4-hydroxyphenyl) benzonitrile and acryloyl chloride were
used as received without further purification. Dibromethane was purchased
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from aladdin reagent company. The purity of all the reagents is AR.
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Synthesis of monomers and its corresponding polymers

For convenience, in this paper, the monomer (4'-cyanobiphenyl-4-oxy) acrylate
was named M0ACB, and the corresponding polymer was named P0ACB. The
monomers with flexible spacer were named MmACB and the corresponding
polymers were named PmACB. The synthetic route of monomers is shown in
Scheme 1. The experimental route is described as follows:
Synthesis of (4'-cyanobiphenyl-4-oxy) acrylate (M0ACB)
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To a mixture of 4-hydroxy-4'-cyanobiphenyl and triethylamine in THF, cooled

to 0℃, was added dropwise acryloyl chloride. The solvent was stirred for 4h.
The reaction solvent was precipitated into ice water, and was filtered and
washed repeatedly with deionized water. The resulting solid was dried to obtain
products as a white solid. H NMR(δ, ppm, CDCl3)：7.74-7.66 (dd, 4H, Ph-H), 7.60

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(d, 2H, Ph-H), 7.36(d, 2H, Ph-H), 6.66-6.62(m, 1H, =CH2), 6.32-6.38(m, 1H, =CH-),
6.07-6.04(m, 1H, =CH2). Mass Spectrometry (MS) (m/z) [M] Calcd for C16H11NO2,

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249.08; [M+H] found 250.
Synthesis of 4'-ethoxybromide-4-cyanobiphenyl

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To a mixture of 4-(4-hydroxyphenyl) benzonitrile, dibromethane, K2CO3 and KI

in actone heat to 80℃，The mixture was stirred for 8h. The reaction solvent was

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precipitated into ice water, and was filtered and washed repeatedly with
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deionized water. The crude products were purified by column chromatography
on silica gel using CH2Cl2 as eluents to give a white powder. 1H NMR (δ, ppm,
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CDCl3):7.71-7.65 (dd, 4H, Ph-H), 7.53 (d, 2H, Ph-H), 7.03 (d, 2H, Ph-H), 4.40-4.29
(m, 2H, -CH2-), 3.73-3.45 (m, 2H, -CH2-). Mass Spectrometry (MS) (m/z) [M] Calcd
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for C15H12BrNO, 301; [M+H] found 302.

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Synthesis of (4- cyanobiphenyl -4'-oxy) ethyl acrylate (M2ACB)

4-(ethoxy bromide)-4'- cyanobiphenyl, acrylic acid and KHCO3 were added in
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300mL DMF. The reaction solvent was heated for 12 h. Then the reaction
solvent was cooled to room temperature. The reaction solvent was poured into
deionized water, and then was filtered. At last, the crude products were purified
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by column chromatograph using CH2Cl2 as eluents. The final product is a white

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solid powder. 1H NMR(δ, ppm, CDCl3): 7.71-7.63 (dd, 4H, Ph-H), 7.55 (d, 2H,
Ar-H), 7.03 (d, 2H, Ph-H), 6.48 (d, 1H, =CH2), 6.21 (m, 1H, =CH2), 5.89 (d, 1H,
=CH2), 4.59(s, 2H, -CH2-), 4.32 (s, 2H, -CH2-). Mass Spectrometry (MS) (m/z) [M]
Calcd for C18H15NO3: 293; [M+H] found: 294.
Synthesis of (4'- cyanobiphenyl-4-oxy) butyl acrylate (M4ACB) The synthetic
method is similar with M2ACB and the 1H NMR data of M4ACB are as follows: 1H
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NMR(δ，ppm，CDCl3)：7.70-7.64 (dd, 4H, Ph-H), 7.53 (d, 2H, Ph-H), 7.00 (d, 2H,
Ph-H), 6.43 (d, 1H, =CH2), 6.14 (m, 1H, =CH2), 5.84 (d, 1H, =CH2), 4.25(s, 2H,
-CH2-), 4.05(s, 2H, -CH2-), 1.91(s, 2H, -CH2-),1.75(s, 2H, -CH2-). Mass Spectrometry
(MS) (m/z) [M] Calcd for C20H19NO3: 321; [M]found: 321.
Synthesis of the polymers

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The polymer was obtained by solution free radical polymerization (see Scheme 1),
and typically carried out as described in the following steps. In a 20mL

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polymerization tube, the monomer and AIBN were dissolved in DMF. The molar
ratio was set with Nmonomer: NAIBN = 100: 1, and the monomer mass concentration was

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35%. After degassed, back-filled three times with N2, the tube was sealed under
vacuum. The polymerization was stirred at 70℃ for 6h. The polymer was then

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purified by re-precipitating from DMF into ethanol.
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Preparation of LCPGs
The binary mixture of gelator and 5CB (the mixture was weighed in at 1.0 g in total)
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were sealed in a screw-capped bottle and heated in magnetic heating sleeve. Allowing
the bottle to stand at 25℃ after the gelator was dissolved completely and then a white
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opaque gel was obtained and it can be kept stable for several months. All other
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LCPGs were prepared via the same method.

Instruments and measurements

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H NMR measurements 1H NMR spectra was recorded on a Bruker ARX400 MHz
spectrometer. CDCl3 or DMSO-d6 were used as solvent and tetramethylsilane (TMS)
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was used as the internal standard.

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Gel permeation chromatography (GPC) The number average molecular weight

(Mn) and polydispersity index (PDI= Mw/Mn) of SCLCPs gelators were measured by
a GPC (PL-GPC 120) instrument. DMF was used as eluent and the flow rate was 1.0
mL min-1 at 80℃.
Differential scanning calorimetry (DSC) measurement Phase transition
temperature of PmACB was obtained by a TA Q10 DSC instrument. The temperature
and heat flow were calibrated using standard materials (indium and zinc) at a cooling
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and heating rates of 10℃min-1.

Minimum gelation concentration (MGC) and gel-to-sol transition temperature
(TGS) measurements the minimum concentration of gelator necessary for gelation is
defined as MGC. The temperature that gel turn into sol is named TGS. The MGC and
TGS of organogels were tested by a “tube-testing method”: A weighted gelator was

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mixed with 5CB in a screw-capped bottle (the samples were weighed at 1.0 g in total)
and the mixture was heated until a transparent solution was formed. The solution was

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cooled at room temperature for 1h. When upon inversion of the screw-capped bottle
no fluid ran down the walls of the bottle, we judged it “successful gelation”.

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Polarized optical microscope (POM) observation Leica DMLM-P microscope
equipped with a Mettler FP82 hot stage and a digital camera was used to observe the

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network structure of LCPGs.
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Scanning election microscope (SEM) observation Scanning electron microscope
(JEOL JSM-6610) was used to observe the microstructures and morphology of
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xerogel. Samples of SCLCPs/5CB were prepared by dropping the gels on Aluminum

foil and were immersed in petroleum ether to extract 5CB for 1 h and then evacuated
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by a vacuum pump at 25℃ for 24h to remove petroleum ether. To minimize sample
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charging, a thin layer of Au was deposited onto the samples before SEM examination.
Rheological measurements Rheological measurements were carried out with a
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stress-controlled rheometer (TA ARES rheometer) equipped with steel parallel-plate

geometry (25 mm diameter). All measurements were tested at 25 °C. Strain sweep at a
constant frequency (1 rad/s) was performed in the 0.01−10% range to measure the
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linear viscoelastic region (LVER) of the gel sample. The frequency sweep was
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obtained from 0.1 rad/s to 100 rad/s at a constant strain of 0.5%. Dynamic
temperature ramp test were performed in the region of 30℃ to 200℃ at 2℃ min-1,
using 25 mm diameter parallel-plate geometry with a frequency of 1 rad s-1 and small
strain amplitude.
Electro-optical response test Electro-optical properties of LCPGs were measured
with indium tin oxide (ITO) liquid crystal cell (The gap of the cell was 8µm). Liquid
crystal or LCPGs was filled into liquid crystal cell by capillary action above TGS.
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Transmission as a function of applied voltage and/or relaxation time was

characterized by an LCD parameter tester (LCT-5016C, North LC Engineering
Research and Development Centre, China) with 1 kHz AC electric field. A halogen
lamp was used as an incident light source. AC electric fields (1 kHz) were applied to
the cells. The threshold voltage (Vth) and saturation voltage (Vsat) were defined as the

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applied voltages required for obtaining 10% and 90% of the maximum transmittance,
respectively. When a voltage is applied (100V), the time required to achieve the 90%

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maximum transmittance is defined as τon and when the voltage is removed, the time
required to reach the 10% maximum transmittance is defined as τoff. The contrast ratio

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(CR) was deduced by calculating the ratio of the maximum transmittance to the
minimum transmittance.

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Results and discussion
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Synthesis and characterization of MmACB and PmACB
The monomers and the corresponding polymers were synthesized referring to the
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synthetic route showed in Scheme 1. The 1H NMR spectra of one representative

polymer P0ACB and its monomer were shown in Fig.1. As can be seen from Fig.1a
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and Fig.1b, the chemical shifts and integral area of peak of all the protons in M0ACB
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are in excellent coincident with its expected structure suggesting that pure monomer
M0ACB was successfully obtained. After polymerization, the proton peaks broadened
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and the characteristic vinyl proton signals of acryl group at 6.66-6.62, 6.32-6.38 and
6.07-6.04 ppm totally disappeared indicating that P0ACB were successfully obtained.
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(a)
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(b)

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Fig.1 1H NMR spectrums of the monomer ACB in CDCl3 (a) and the polymer
PmACB in DMSO-d6 (b)

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The number average molecular weight and polymer distribution index of all
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polymers were measured by GPC. The results were shown in Table 1. All polymers
have high enough molecular weight and narrow polymer distribution index to remove
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the influence of Mn and PDI on the properties of LCPGs. The thermal stability and
liquid crystal phase behavior of all polymers were characterized by TGA and DSC.
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The test curves were shown in Fig.2. All polymers have good thermal stability, the
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thermal decomposition temperature is above 300℃ (see Table 1). Fig.2 (b) shows
the second heating DSC curves of polymers. All polymers show two distinct peaks
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which corresponding to glass transition temperature (Tg) and clear point temperature
(Ti). The liquid crystalline phase structure of all polymers has been reported [36-38],
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and therefore we did not characterize it furtherly.

Table 1 the properties of polymers
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Polymer Mn(×104)a PDIa Td(℃)b Ti(℃)c Tg(℃)d

P0ACB 4.91 2.5 344 282 152
P2ACB 6.86 2.9 368 97 85
P4ACB 8.62 2.5 359 123 58
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Obtained from PL-GPC 120 instrument, linear PS as standards.
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The temperatures at 5% weight loss of the samples under nitrogen (Td(N2)) were measured by

TGA heating experiments at the rate of 10℃min-1.

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The transition temperature from liquid crystalline phase to isotropic phase measured by DSC
at a heating rate of 10℃min-1 under nitrogen atmosphere during the second heating process.
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d
The glass transition temperatures were measured by DSC at a heating rate of 10℃min-1
under nitrogen atmosphere during the second heating process.

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Fig.2 TGA curves of polymers PmACB (a) and the second heating DSC curves of
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polymers PmACB (b)

Gelation ability of SCLCPs and thermal properties of LCPGs
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The solubility and gelling abilities of PmACB were tested by “tube-testing method”.
The SCLCPs with flexible spacer (P2ACB, P4ACB) were dissolved in 5CB during
the heating process, and it failed to form gel when cooled to room temperature. Even
the amount of polymer was increased to 10wt%, the polymer with flexible spacer
could not form gel in 5CB. P0ACB can form stable gels in 5CB and the minimum
gelation concentration was 1wt%. In the process of LCPGs formation, gelators need
to carry out three processes: molecular recognition, unidirectional aggregation of fiber
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and the intertwining fibrous objects to form gel network structure. The main chain of
SCLCPs with flexible spacer (P2ACB, P4ACB) has little effect on the side chain
group and cyanobiphenyl group is similar to 5CB structure, and therefore the SCLCPs
with flexible spacer are dissolved and fail to form gel network structure in 5CB. The
main chain of the SCLCPs without the flexible spacer (P0ACB) can reduce the

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compatibility of side chain groups with 5CB, and thus the side chain groups of
P0ACB can self-assemble into gel network structure by the π- π interaction.

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Thermal behaviors of LCPGs P0ACB/5CB were investigated by using the
“tube-testing method” to measure the transition temperature (TGS) from gel to solution.

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As can be seen in Fig.3, the LCPGs is white opaque gel at room temperature, when
the temperature rises to the clear point of 5CB (35℃), it becomes a translucent gel, as

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the temperature increases to TGS, the gel is completely destroyed and transformed into
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colorless transparent liquid. The TGS values depend on the concentration of gelators.
As can be seen in Fig.4, the TGS of P0ACB/5CB gel increased sharply with increasing
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the concentration of P0ACB in 5CB and cannot be improved anymore until the mass
fraction exceeds 6.0wt%. It can be seen from the above results that the P0ACB/5CB
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has good self-supporting ability in the heating process. This self-supporting ability is
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obviously superior to the previously reported small molecular LCPGs. It may be

explained that the P0ACB can not only form the gel network through the π-π
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interaction of the side chain group, but also the main chain entanglement can further
strengthen the gel network structure.
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Fig.3 The formation of the P0ACB/5CB LC physical gel

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Fig.4 The gel-sol transition temperature of LCPGs P0ACB/5CB
Microstructure of LCPGs

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The microstructure of P0ACB/5CB was observed by polarizing microscope. As can
be seen from Fig.5, with the increase of temperature, the polarized image of P0ACB/

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5CB has changed obviously. When the temperature is lower than the clear point of
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5CB, the gel has obvious birefringence phenomenon. This implies that the anisotropy
of the liquid crystals (5CB) is not destroyed by the networks of gelators. As the
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temperature rises above 40℃, many dark regions appear in the field of view, but the
birefringence can still be observed, meaning that the ordered structure of the gelators
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still exists in the LCPGs. As the temperature increased to 120℃, birefringence can
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still be observed in photos, indicating that the gel network structure can still keep at a
high temperature. Finally, the field becomes dark after the temperature rises to TGS,
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meaning that the gel network structure was destroyed at TGS. The above results
indicated that LC gel formed by the polymer P0ACB does not destroy the liquid
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crystalline property of 5CB, and the gel network exhibited excellent thermal stability.
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In addition, the microstructure of the P0ACB gel was studied by FE-SEM. Fig.6
shows the xerogel of the 3wt% P0ACB/5CB after remove LC host. It can be clearly
seen from the pictures that the polymer gelators formed a fiber-like network structure
with small diameter. Due to the stronger surface tension and capillarity of fiber-like
network, 5CB can be anchored tightly and formed stable gel.
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Fig.5 POM image of 3wt% P0ACB/5CB at 30℃(a) and 40℃(b); POM image of 3wt%
P0ACB/5CB at 120℃(c) and TGS (d).
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Fig.6 FE-SEM images of xerogel after remove the LC host. (a) xerogel with 3wt%
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P0ACB (scale bar is 5µm). (b) xerogel with 3wt% P0ACB (scale bar is 1µm).
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Mechanical properties of LCPGs

The mechanical properties of LCPGs were characterized by rheological
measurements. Storage modulus (G') is a critical parameter to estimate
mechanical strength of LCPGs and can evaluate the the degree of resistance of
the LCPGs against mechanical disturbance. Loss modulus (G") measures the
tendency of LCPGs to flow under stress.
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In order to study the rheological properties of the gel, the linear regime of the
storage modulus (G') and loss modulus (G") of LCPGs must be measured first as
functions of shear strain. As shown in Fig.7(a), in the strain range from 0.1% to 1%,
the G' always larger than G", meanwhile G' and G" remained approximately
constant during this strain range indicating that this region is defined as the

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linear viscoelastic region of the LCPGs. When the shear strain value is greater
than 1%, the G' and G" of LCPGs decreased sharply with increase the shear

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strain. When the strain value is greater than 3.5%, the decrease of the modulus of
G' is observed, indicating that the LCPGs collapsed and lost its mechanical

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properties.
To further detect the resistance of the gel material to the external stress,

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frequency sweeps test were conducted. Frequency sweeps were tested at low
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strain (0.5%), which within the linear viscoelastic region. As can be seen in
Fig.7(b), the G' and G" of 3wt% P0ACB/5CB LCPGs have a slight dependence
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on the frequency in the frequency range of 0.1-100 rad/s. G' remained larger
than G"and there was no crossover throughout the whole frequency, indicating
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that the LCPGs has a good tolerance to external forces.

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The effect of temperature on the mechanical properties of 6.0wt% P0ACB/5CB

LCPG was measured by dynamic temperature ramp test. As can be seen from the Fig
7(c), the storage modulus of 6.0wt% P0ACB/5CB is more than 104 Pa at 35℃.In
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the temperature range from 30℃ to 170℃, G' and G" value decrease steadily, but
still remained G' larger than G" and the G' was about 104Pa. This result indicates
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that the solid state characteristics of the LCPGs begin to be lost. When the
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temperature reaches 170℃, G' and G" began to decrease dramatically, meanwhile, G"
is slightly larger than G'. It implies that the solid-state properties of LCPGs
completely disappear. The dynamic temperature ramp test results are inconsistent with
“tube-testing method” results. The reason is that the external pressure has a certain
destructive effect on the LCPGs in rheological testing.
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(a)

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(c)

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Fig.7(a) Strain dependence of storage modulus (G') and loss modulus (G") for 3wt%

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P0ACB/5CB at room temperature; Condition: ω=1rad/s. (b) Frequency dependence of
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G' and G" for 3wt% P0ACB/5CB at room temperature; Condition: 0.5% strain; (c)
Temperature dependence of G' and G" for 6wt% P0ACB/5CB from 30℃ to 200℃.
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Condition: 0.5% strain, 1 rad s-1 frequency and 2℃ min-1 heating rate.
Electro-optical properties of LCPGs
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Based on the above characterization, we can find that P0ACB can form LCPGs in
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5CB, and the LCPGs exhibited excellent thermal stability and mechanical properties.
But we don't know whether the introduction of the SCLCPs will affect the
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electro-optical properties of 5CB. Therefore, we tested the electro-optical properties

of PmACB/5CB composites. Test results are shown in Table 1. As we can see from
the table, the SCLCPs without gelation ability (P2ACB and P4ACB) had little
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influence on their electro-optical properties. However, the addition of P0ACB

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increased the driving voltage of 5CB but the open response time (τon) was almost
unchanged, and the off state response time (τoff) was reduced. Among the reported
LCPGs [24, 27, 38, 39], the driving voltage of LCPGs is greater than that of pure 5CB
due to the anchoring effect of gelators on 5CB. In addition, the gel network structure
formed by small molecular gelators is rigid fiber network, which may hinder the
orientation of 5CB under the electric field. After removing the electric field, the rigid
fiber network structure also affect the recovery process of 5CB. Thus, the addition of
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small molecular gelators increase the τon and the τoff of LCPGs. Hereon, the anchoring
effect of P0ACB also leads to an increase in the driving voltage of the LCPGs.
Interestingly, the structure of the gel network formed by P0ACB is flexible and the
side chain group of the P0ACB is similar to 5CB. Under the application of 100V
voltage, the flexible gel network permit the orientation of side group, and therefore

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the addition of P0ACB will not impede the orientation speed of 5CB and not affect
the τon of 5CB. When the voltage is removed, there is strong anchoring energy

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between the side chain group and 5CB, the recovery of oriented side group can help
5CB back to its original state, which will cause the reduced τoff. This part of the work

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will be further explored in the future research.
Table 2 Electro optic parameters of 3wt% SCLCPs/5CB LCPGs and 5CB

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Simple Vth(V µm-1) Vsat(V µm-1) CR τon(ms) τoff(ms)
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P0ACB/5CB 0.290 3.906 5.28 0.112 6.748
P2ACB/5CB 0.164 0.239 4.23 0.110 7.232
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P4ACB/5CB 0.165 0.236 4.32 0.104 8.096

5CB 0.168 0.239 4.15 0.112 8.758
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The influence of P0ACB addition on the electro-optical properties of LCPGs was

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also investigated. With the increase of P0ACB concentration, the electro-optic

parameters of LCPGs changed. The electro-optical response test results of
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P0ACB/5CB are shown in Fig.8 and the test results were summarized in Table 3. All
the LCPGs with different P0ACB addition showed high contrast, and with the
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increase of gelators concentration, the contrast increased significantly. This

phenomenon was attributed to the light scattering effect of the gelators. At the same
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time, the threshold voltage (Vth) and saturation voltage (Vsat) also increased with the
increase of concentration. This is because the higher concentration of P0ACB leads to
higher gel network density and higher anchoring energy which makes the orientation
of 5CB more difficult in the gel when applied voltage. The response speed of the
electric is another important parameter. As we can see in Table 3, with the addition of
P0ACB in the LCPGs, The response time of the open state (τon) is consistent with the
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response time of pure 5CB, while the response time of the off state (τoff) decreased.
Similar to the above reasons, with the increase of the concentration of gelators, 5CB
are anchored stronger, after the withdrawal of the electric field, the anchoring effect of
the P0ACB is favorable for going back to their original position quickly. LCPGs of
6.0wt% P0ACB/5CB was chosen as a typical sample to estimate fatigue resistance. As

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shown in Fig.9, after many switching under 100V, there is no obvious deterioration in
electro-optical properties of LCPGs indicating that the prepared LCPGs had good

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fatigue resistance.
Table 3 Electro-optic parameters of P0ACB/5CB gel

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Simple Vth(V µm-1) Vsat(V µm-1) CR τon(ms) τoff(ms)
0wt% 0.168 0.239 3.71 0.112 8.758

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1wt% 0.203 0.336 4.08 0.113 7.265
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2wt% 0.254 0.353 4.82 0.106 7.058
3wt% 0.290 3.906 5.28 0.112 6.748
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4wt% 0.306 4.215 6.15 0.109 6.258

5wt% 0.319 4.308 7.05 0.113 5.345
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6wt% 0.327 7.191 8.59 0.123 5.275

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Fig.8 Electro-optic response curves of P0ACB/5CB gels

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Fig.9 The electro-optical response of LCPGs with 6.0 wt% P0ACB/5CB (100 V).
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In order to further explore its application on the display material, the LCPGs were
injected into a liquid crystal cell with a thickness of 8µm above the temperature of
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TGS. When the temperature was cooled to room temperature, the liquid crystal cell
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becomes blurred and opaque. It can be seen from Fig. 10. When the voltage of 100V
was applied, the liquid crystal cell with conductive coating (1cm2) becomes
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transparent and in the light transmission state. Such intense light and shade contrast
effect endow it with wide range of applications in display material.
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Fig.10 The electro-optic response test of 3.0wt% P0ACB/5CB LCPGs with a

thickness of 8µm

Conclusion
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In this article, we have prepared a series of high performance LCPGs with

excellent thermal stability, good self-support ability, and fast electro-optical
response properties based on side chain liquid crystal polymers. The thermal
stability of LCPGs was measured by “tube-testing method”. The test results showed
that the LCPGs by P0ACB has high TGS, and the TGS increases with the increase of

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concentration, but tends to be stable after the concentration exceeds 6wt%. It can be
seen from the rheological test that LCPGs exhibit good self-supporting ability with a

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storage modulus higher than 104Pa. LCPGs (P0ACB/5CB) have unprecedented
excellent performance. It was found that the threshold voltage and saturation voltage

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of LCPGs with 3wt% P0ACB were 0.290 V µm-1 and 3.906 V µm-1 respectively. The
open state response time of pure 5CB is 0.112ms. Even the amount of the polymer is

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increased to 6wt% in the LCPGs, it open state response time is only 0.123ms. The
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addition of polymer gelators does not affect the open response time of 5CB, which
has never been reported before. On the contrary, the addition of polymer gelators
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could reduce the response time of its off state. These superior properties give it a great
advantage in the field of optoelectronic materials. In addition, compared with the
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small molecular gelators, the SCLCPs have many advantages as the gelators. The
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LCPGs prepared by SCLCPs can control its mechanical properties and electro-optical
response properties by changing the types of side groups, controlling molecular
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weight and copolymerization. Hence, this study is very important for future study of
LCPGs using SCLCPs gelators. More importantly, this study is helpful to understand
the effect of the anchoring effect of the gelators on the properties of the LCPGs.
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Funding: This work was supported by National Natural Science Foundation of

China (No. 51573152, 51373148). Open Fund Project of Innovation Platform in
Colleges and Universities of Hunan Province (16K085).

Notes and references

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Highlights
1. A liquid crystalline physical gel prepared by side chain liquid crystalline polymers is provided.
2. A liquid crystalline physical gel prepared by side chain liquid crystalline polymers show
excellent thermal stability, good self-supporting ability and fast electro-optical response
properties.
3. The addition of the polymer does not affect the electro-optical response of the LCPGs.

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