Side-chain Liquid Crystal Polymers Research Articles

Liquid crystallinity and magnetorheological performance of polymeric liquid crystal magnetic composites

ABSTRACT Magnetorheological fluids (MRF) are regarded as a novel ‘intelligent’ material because they show the ability to respond to external stimuli. However, with the extension of working time, the agglomeration and sedimentation of magnetic particles become a serious problem, which has a great impact on the magnetorheological performance. Many methods have been proposed to overcome the particle settling problem, including magnetic particle modification and carrier liquid modification, but they all show negative effects on the magnetorheological performance of MRF. A new method to prepare the magnetic liquid crystal (LC) composites [PEA-COOH]SO3H@Fe3O4 series, with Fe3O4 nanoparticles as core and side-chain supramolecular LC polymers with different mesogen contents as coating, were reported. The chemical structure, magnetic property and LC properties were investigated by a variety of techniques. In order to study the effects of the mesogen content and LC phase state of magnetic LC composites on magnetorheological performance and sedimentation stability, MRF based on silicone oil carrier liquid and [PEA-COOH]SO3H@Fe3O4 dispersed phase were prepared. It was found that dynamic yield stress, plastic viscosity and the sedimentation ratio increased slightly with increasing mesogen content in the magnetic LC composites. What’s more, MRF prepared by magnetic LC composites annealed in LC state exhibited better magnetorheological performance and sedimentation stability than those in glassy state and isotropic state. These results indicated that the synergetic effects of LC orientation and magnetic field-induced arrangement of Fe3O4 magnetic particles can improve the magnetorheological performance and sedimentation stability of MRF.

Impact of Molecular-level Structural Disruption on Relaxation Dynamics of Polymers with End-on and Side-on Liquid Crystal Moieties.

In side-chain liquid crystal polymers (SCLCPs), short side chains are attached on a flexible polymer backbone, and each side chain can have a liquid crystal (LC) group attached at the final bead in either an end-on or a side-on configuration. SCLCPs with random sequences of end-on and side-on LC moieties exhibit nonmonotonic thermal behavior as a function of composition, with some mixed sequences having a lower isotropic to LC phase transition than either purely end-on or side-on configurations. The origin of this nonmonotonic thermal trend lies in the disruption of molecular-level positional ordering and alignment due to the different preferred types of ordering of the different LC attachment types. We compare coarse-grained molecular dynamics (MD) simulations and experiments on SCLCP systems with only one type of LC moiety and demonstrate qualitative agreement in the observed mesophases of end-on and side-on SCLCP systems. Specifically, end-on SCLCPs display a smectic B-like mesophase, with layers of polymer between LC layers, while side-on SCLCPs exhibit a quasi-hexagonal columnar structure of polymer and a nematic surrounding the LC mesophase. Detailed analysis of SCLCP systems with various compositions of these types of LC attachments via MD reveals structural disruption in systems with intermediate compositions. Simulation snapshots and anisotropy ratio measurements show how random SCLCP systems deviate from the expected behavior of prolate or oblate systems in terms of their conformation. This molecular disruption in random SCLCP systems, particularly with a high composition of side-on LC moieties, also significantly impacts the relaxation dynamics. Modifying the composition of the LC type of attachment (molecular structure) is a possible route to tuning both the phase behavior and mechanical response of these systems.

Preparation and properties of novel liquid crystal ionomers bearing benzoxazole-based mesogenic side-chains and their membranes

A new heterocyclic mesogenic compound, 6-[4-(5-chloro-2-benzoxazolyl)phenoxy]-hexanethiol (CBPHT), is designed and synthesized, which shows an enantiotropic SmC mesophase with the liquid crystal phase ranges of 5.67 °C and 22.99 °C on heating and cooling, respectively. The CBPHT-based side-chain liquid crystal polymers (LCP-x) are obtained via a nucleophilic substitution between CBPHT and polyepichlorohydrin, and also shows an enantiotropic SmC mesophase with narrow temperature range. Furthermore, novel side-chain liquid crystal ionomers (LCI-x) with enantiotropic SmC mesophase are prepared via quaternization of N-methylimidazole with LCP-x, where polyepichlorohydrin, CBPHT and methylimidazolium chloride act as polymer main-chain, mesogenic side-chain, and ionic group, respectively. In addition, LCI-x membranes can be fabricated via a solution casting method, and exhibit high thermal stability, good mechanical properties and high ion conductivity. For example, LCI-0.20 with a low ion exchange capacity of 0.12 mequiv. g−1 has a large elongation at break (385 %) and a high chloride ion conductivity (20.68 mS cm−1), indicating a high potential for application as polymer electrolyte membrane.

Clustering-Triggered Emission Liquid Crystalline Polymer Bearing Cholesterol: Tunable Circularly Polarized Luminescence and Room-Temperature Phosphorescence.

Circularly polarized luminescence (CPL) materials with clustering-triggered emission (CTE) characteristic have gradually attracted attention for their unique photophysical properties. However, the majority of reported clusteroluminogens lack chirality and exhibit heterogeneity, making it challenging to achieve a well-defined helical structure necessary for efficient CPL with high dissymmetry factor (glum ). In this paper, chiral liquid crystals are constructed to obtain CTE-based CPL materials with high glum values. Side chain liquid crystal polymer PM6Chol bearing cholesterol clusteroluminogens are designed and synthesized. PM6Chol-coated film and PM6Chol thermal-treated film are also successfully prepared by different film-forming methods. Both the films inherit the CTE characteristic of cholesterol and show excitation wavelength-dependent luminescent behavior. However, the two polymer films exhibit different liquid crystal phase structures, with PM6Chol-coated film being a chiral bilayer smectic C phase and PM6Chol thermal-treated film being an achiral bilayer smectic A phase. Attributed to helical arrangement of cholesterol, PM6Chol-coated film emits efficient CPL with glum values up to 1.0 × 10-1 . For PM6Chol thermal-treated film, no CPL signal is detected due to the absence of helical structure. However, it shows obvious room-temperature phosphorescence with 2.0 s afterglow and 23.9ms lifetime.

The relaxation dynamics and dielectric properties of cyanobiphenyl-based nematic tripod liquid crystals

We present a detailed investigation of the phase behaviour, molecular relaxation dynamics, rheology and dielectric properties of two cyanobiphenyl-based liquid crystal (LC) tripods, differing only in the length of their spacer units (6 or 9 carbons). These LC tripods combine properties of low molecular weight LCs and LC polymers, resulting in a range of advantageous properties including a wide nematic range (ΔT>90 K) and a large birefringence (0.3 at T−TNI=-80 K for the 6 spacer tripod). Using broadband dielectric relaxation spectroscopy, calorimetry, oscillatory and steady state shear rheology, we identified four molecular relaxation processes: the structural (α) relaxation (defining the glass transition temperature, Tg); the δ relaxation (reorientation of the mesogen unit around its short axis); the β relaxation (reorientation around its long axis); and the γ relaxation (internal tripod arm fluctuations). The β and γ relaxations follow Arrhenius temperature dependencies in the glass, whereas the α and δ relaxations merge above, but near Tg, where they follow a non-Arrhenius VFT behaviour. For higher temperatures, the two relaxations separate and for T>T⁎, where T⁎ marks a dynamic crossover, the α relaxation transitions from VFT to Arrhenius behaviour. For the two tripods, ratios of T⁎/Tg=1.14 and T⁎/Tg=1.13 were observed respectively, consistent with the ratio observed for many side-chain LC polymers (and other LC systems), and consistent with the ratio where a dynamic crossover is typically observed also for non-LC glass-formers. However, for non-LC systems, the transition to Arrhenius behaviour happens at significantly higher temperatures relative to Tg and the dynamic crossover at T⁎ is typically observed as a transition between two different VFT behaviours. We argue that for the tripods these differences arise from differences in the molecular relaxation mechanisms induced by the LC order. Finally, for temperatures where δ and α relaxations are separated, we find that ion conductivity decouples from the α relaxation, instead following the δ relaxation; this demonstrates that the ion transport properties for the tripods can be tuned by the design of the tripod mesogen arm.

Synthesis and mesomorphic properties of novel multi-arm side-chain liquid crystal polymers with different terminal substituents

ABSTRACT In this study, two novel aromatic ester multi-arm liquid crystal monomers M 1 and M 2 with different terminal substituents centred on 3,4,5-trihydroxybenzoic acid, and a rod-shaped chiral liquid crystal monomer N were designed and synthesised. The synthesised liquid crystal monomers M and N were grafted and copolymerised with polymethylhydrosiloxane (PMHS). The structural characterisation of the synthesised liquid crystal compounds was carried out by FT-IR and 1H-NMR. The mesomorphic properties of the synthesised liquid crystal compounds were characterised by POM and DSC, and the results showed that the multi-arm liquid crystal monomers M 1 and M 2 are typical enantiotropic nematic liquid crystal compounds and N is typical thermotropic enantiotropic cholesteric liquid crystal. Polymers P 1 and P 2 are both cholesteric liquid crystal polymers. The glass transition temperatures and liquid crystal isotropic transition temperatures of polymers P 1 and P 2 series both tend to increase with the increase of multi-arm liquid crystal monomer M.

Synthesis and mesomorphic properties of swallow-tailed liquid crystal monomers and polymers

In this article, we designed and synthesized two novel swallow-tailed liquid crystal monomers (M1 and M2) with different chain lengths and rigidities centered on 3,4,5-trihydroxybenzoic acid and two series of side-chain liquid crystals polymers PN1 and PN2. All liquid crystal monomers and polymers were conformed to the molecular designs by FT-IR and NMR. The liquid crystal properties were tested by DSC and POM, and the results showed that M1 and M2 were thermotropic enantiotropic nematic liquid crystals and the side-chain liquid crystal polymers PN1 and PN2 series were typical amorphous liquid crystal polymers. With the increase of monomer content, the glass transition temperatures and clearing points of PN1 and PN2 series enhanced. With the increase of the number of mesogens in the liquid crystal monomer, the rigidity was enhanced, and the liquid crystal performance of the polymer was better.

Coarse-grained modeling of polymers with end-on and side-on liquid crystal moieties: Effect of architecture.

Mesogens, which are typically stiff rodlike or disklike molecules, are able to self-organize into liquid crystal (LC) phases in a certain temperature range. Such mesogens, or LC groups, can be attached to polymer chains in various configurations including within the backbone (main-chain LC polymers) or at the ends of side-chains attached to the backbone in an end-on or side-on configuration (side-chain LC polymers or SCLCPs), which can display synergistic properties arising from both their LC and polymeric character. At lower temperatures, chain conformations may be significantly altered due to the mesoscale LC ordering; thus, when heated from the LC ordered state through the LC to isotropic phase transition, the chains return from a more stretched to a more random coil conformation. This can cause macroscopic shape changes, which depend significantly on the type of LC attachment and other architectural properties of the polymer. Here, to study the structure-property relationships for SCLCPs with a range of different architectures, we develop a coarse-grained model that includes torsional potentials along with LC interactions of a Gay-Berne form. We create systems of different side-chain lengths, chain stiffnesses, and LC attachment types and track their structural properties as a function of temperature. Our modeled systems indeed form a variety of well-organized mesophase structures at low temperatures, and we predict higher LC-to-isotropic transition temperatures for the end-on side-chain systems than for analogous side-on side-chain systems. Understanding these phase transitions and their dependence on polymer architecture can be useful in designing materials with reversible and controllable deformations.

Precisely Controllable Artificial Muscle with Continuous Morphing based on "Breathing" of Supramolecular Columns.

Skeletal muscles are natural motors executing sophisticated work through precise control of linear contraction. Although various liquid crystal polymersbased artificial muscles havebeen designed, the mechanism based on mainly the order-disorder transition usually leads to discrete shape morphing, leaving arbitrary and precise deformation a huge challenge. Here, one novel photoresponsive hemiphasmidic side-chain liquid crystal polymer with a unique "breathing" columnar phase that enables continuous morphing is presented. Due to confinement inside the supramolecular columnar assembly, the cooperative movements of side-chains and backbones generate a significant negative thermal expansion and lead to temperature-controllable muscle-like elongation/contraction in the oriented polymer strip. The irreversible isomerization of the photoresponsive mesogens results in the synergistic phototunable bending and high-contrast fluorescence change. Based on the orthogonal responses to heat and light, controllable arm-like bending motions of this material, which is applicable in constructing advanced artificial muscles or intelligent soft robotics, are further demonstrated.

Preparation and properties of light-triggered self-healing form-stable phase change materials

Light-triggered self-healing form-stable phase change materials (FSPCMs) can not only store and release thermal energy, but can also realize self-healing performance under light, showing important practical values. In this article, we provided a new strategy for the preparation of FSPCMs with light-triggered self-healing ability and high thermal energy storage density. Azobenzene side chain liquid crystal polymer was synthesized and used as gelator to blend with paraffin, and then the mixture was heated and dissolved to form transparent solutions. FSPCMs could be obtained after natural cooling to room temperature. The thermal stability, energy storage capacity and rheological property of the prepared FSPCMs were studied in detail. With the increase of gelator content, the thermal stability and storage modulus of FSPCMs enhanced, while the energy storage density decreased. When the gelator content is 6.0 wt%, the gel-sol phase transition temperature (TGS) of the FSPCM was 127 °C, the storage modulus could achieve 2.3 × 103 Pa at 70 °C, and the phase change enthalpy was 193.1 J g−1, showing excellent self-supporting performance and higher energy storage density. More interestingly, the FSPCMs also showed excellent light-triggered self-healing ability. When the FSPCMs were damaged, the materials could quickly repair the damage under the sequential irradiation of 365 nm and 470 nm light.

The simultaneous control over the alternating sequence and the inner-core position of the mesogenic segments in side-chain liquid crystal polymers

Hydrosilylated 1,1-diphenylethylene (DPE-SiH/2SiH) are herein quantitatively and alternatingly incorporated during the living anionic copolymerization of isoprene with DPE-SiH/2SiH, which can efficiently control the Si-H densities and positions. The diversified mesogenic moieties containing azobenzene (Azo) or trifluoromethyl (F3C) groups, respectively, with the tuned inner-core position of the mesogenic segments are rationally designed and then fabricated into multiple alternatingly-arranged side-chain liquid crystal polymers (SCLCPs) along the alternating backbones. This study presents the novel SCLCPs with the simultaneous control over the sequence and the inner-core position of the mesogenic segment, providing the promising route and study model to develop the mechanistic investigations. The temperature range of mesomorphic phase formation (ΔT) and polarized optical morphologies are proved to be synergistically dependent on the diversified mesogenic moieties and the exactly controlled densities of the mesogenic segment.

Effect of chiral monomer containing D(+)-camphoric acid on the optical properties and phase behaviours of side-chain cholesteric liquid crystal polymers

ABSTRACT Cholesteric liquid crystals with selective reflection have important applications in the field of light control and optical thin films. In this study, a series of side-chain cholesteric liquid-crystal polymers (named as PPL series) was synthesised by a one-step hydrosilylation reaction among monomer LA containing cholesterol group, monomer LB containing D(+)-camphoric acid group and monomer LG containing cyano group. The chemical structures and the mesogenic properties of the monomers and polymers were determined by usual test methods. Testing results showed that PPL series polymers had excellent thermal stability and wide range of mesophases. As the content of monomer LB increased, PPL1-PPL6 could be observed colourful Grandjean textures and good selective reflection. The optical rotation experiment indicated that the rotation direction of the PPL series was consistent with that of the monomer LB, and the specific rotation was linearly related to the content of the monomer LB.

A simple engineering strategy with side chain liquid crystal polymers in perovskite absorbers for high efficiency and stability

Abstract Accomplishing a superior perovskite layer with better morphology, enhanced efficiency, and improved stability is one of the great challenges to researchers. In present work, we incorporated various side chain liquid crystal polymers (SCLCP) as dopants into the perovskite precursor to attain high efficiency and long-term stability of the perovskite solar cells (PSCs). Incorporation of SCLCP increases the grain size of the crystalline perovskite film by controlled solvent evaporation, decreased the grain boundaries and reduced charge recombination, which decelerates the material degradation. With the SCLCP doping, the PSC power conversion efficiency was expressively enhanced from 17.8% (non-doped) to 19.01% for the doped perovskite film with much improved stability. Furthermore, the atomic force microscopy measurements showed a better surface roughness for doped film by effective passivation of the perovskite grain surfaces. Field emission scanning electron microscope also showed better morphology with reduced grain boundaries. Especially, the SCLCP act as bridge between the crystal grains for efficient charge transfer from perovskite layer towards the electrode, which would moderately illustrate the increased efficiency and stability.

Synthesis and mesomorphic properties of H-bonded side-chain liquid crystal polymers of two modifications of poly(4-vinylphenol) and poly(4-vinylpyridine)

Poly(4-vinylphenol) was modified to poly(4-(4-vinylphenoxy)butan-1-ol) and poly(4-(6-(4-vinylphenoxy)hexyloxy)benzoic acid). Methyl 4-((E)-2-pyridin-4-yl)vinyl)benzoate ligand was synthesized and hydrogen bonded with two modified polymers. Complexes of poly(4-vinylpyridine) with another series of ligands, 6-hydroxyhexyl 4-(E)-4-alkoxy)styry)benzoates, have also been prepared. The liquid crystalline properties of the blends have been investigated using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Complexes of methyl 4-((E)-2-pyridin-4-yl)vinyl)benzoate with the two modified polymers show grainy texture of nematic phase, whereas the complexes of poly(4-vinylpyridine) with styrylbenzoate ligands exhibit smectic phases.

Synthesis of well-defined PS-based Azo-liquid crystals with control of phase transitions and photo-behaviors for liquid crystal networks with photomechanical deformation

Benefiting from their good mechanical processability and high tunability, Si–H and vinyl-functionalized polystyrenes (PSs), i.e., poly(4-vinylphenyl)-dimethyl-silane (PVPDMS/PS-SiH) and poly(4-vinylphenyl)-1-butene (PVSt/PS-Vinyl), produced by living anionic polymerization (LAP) were treated with four vinyl- and Si–H-terminated azobenzene mesogens (Azo-Vinyl, Azo-SiH, AzoB-Vinyl, and AzoB-SiH, referred to as M1, M2, M3, and M4, respectively) via hydrosilylation for the fabrication of PS-based side-chain liquid crystal polymers (SCLCPs) containing different spacers, i.e., PS-SiC/SiOSi-Azo/AzoB. As a strategy for basic molecular control in PS-based SCLCPs, the cooperative influences of the spacers and the degree of polymerization (DP) on the mesomorphic transitions were explored. The phase transitions could be tuned slightly based on the DP but dramatically by adjusting the spacers. For example, the temperature ranges of mesomorphic formation (ΔT) were in the order PS-[SiOSi]-Azo (ΔT = 34–49 °C) < PS-[SiC]-Azo (ΔT = 49–60 °C) < PS-[SiOSi]-AzoB (ΔT = 154–164 °C) < PS-[SiC]-AzoB (ΔT = 162–193 °C). Taking advantage of the quantitative structure-property correlation of PS-based SCLCPs, PS-based liquid crystal networks (LCNs) were further designed for the photomechanical deformation. PS-based LCNs show good mechanical properties with a storage modulus of 120 MPa, controlled phase transitions, and glass transition temperatures (Tg) around room temperature. Crosslinked PS-based LCNs of rigid PS homopolymers with selective crosslinking can exhibit directional bending upon irradiation with UV light at 50 °C after stretching, and this was shown to be a photomechanical deformation, which expands the applicability of these materials.

Cholesteric fluorescent liquid crystal polysiloxanes with different liquid crystal side chain lengths—Synthesis and properties

With polymethylhydrogensiloxane (PMHS) as the main chain, two series side-chain cholesteric liquid crystal polymers (ChLCPs) with different liquid crystal side chain lengths were prepared by hydrosilylation reaction. Then two series of cholesteric fluorescent liquid crystal polymers (FL-ChLCPs) were obtained by etherification reaction. The obtained FL-ChLCPs have both excellent mesomorphic behavior, and great photoluminescent property. We confirmed their chemical structures by FT-IR, and 1H NMR spectroscopy, and found them with excellent thermal stability by TGA. We characterized their mesomorphic behavior and thermal performance by POM, DSC and XRD, and confirmed all the polymers belonged to cholesteric phase. FL-ChLCPs emitted different-intensity fluorescence under UV light, and we found some regularity by PL spectrum.

Design and Synthesis of Polysiloxane Based Side Chain Liquid Crystal Polymer for Improving the Processability and Toughness of Magnesium Hydrate/Linear Low-Density Polyethylene Composites.

In this study, a polysiloxane grafted by thermotropic liquid crystal polymer (PSCTLCP) is designed and synthesized to effectively improve the processability and toughness of magnesium hydroxide (MH)/linear low-density polyethylene (LLDPE) composites. The obtained PSCTLCP is a nematic liquid crystal polymer; the liquid crystal phase exists in a temperature range of 170 to 275 °C, and its initial thermal decomposition temperature is as high as 279.6 °C, which matches the processing temperature of MH/LLDPE composites. With the increase of PSCTLCP loading, the balance melt torque of MH/LLDPE/PSCTLCP composites is gradually decreased by 42% at 5 wt % PSCTLCP loading. Moreover, the power law index of MH/LLDPE/PSCTLCP composite melt is smaller than 1, but gradually increased with PSCTLCP, the flowing activation energy of PSCTLCP-1.0 is lower than that of MH/LLDPE at the same shear rate, indicating that the sensitivity of apparent melt viscosity of the composites to shear rate and to temperature is decreased with the increase of PSCTLCP, and the processing window is broadened by the addition of PSCTLCP. Besides, the elongation at break of MH/LLDPE/PSCTLCP composites increases from 6.85% of the baseline MH/LLDPE to 17.66% at 3 wt % PSCTLCP loading. All the results indicate that PSCTLCP can significantly improve the processability and toughness of MH/LLDPE composites.

Finger-Temperature-Detecting Liquid Crystal Composite Film for Anti-Counterfeiting Labels.

The development of the economy has increased the demand for anti-counterfeiting technologies, and with the traditional ones becoming known to the public, new and more effective ones are needed. In this study, a series of liquid crystal mixtures containing side-chain liquid crystal polymers and small-molecular-weight liquid crystals (LCs) were designed and prepared. The phase transition behavior and self-assembling structures of the LC mixtures were investigated by a combination of differential scanning calorimetry, polarized optical microscopy, and small-angle X-ray diffraction. The optical properties of the mixture film were characterized with a UV/VIS/IR spectrum study. The results reveal that the obtained film exhibited different optical modes between transparent, scattering, and selective reflection under finger-temperature control. Therefore, by the introduction of a coexisting thermal- or optical-polymer-dispersed network, a liquid crystal composite film with an integration of apparent optical switching modes and enhanced strength and toughness was successfully demonstrated. This research provides a versatile strategy for the design and preparation of liquid crystal anti-counterfeiting materials for practical use. In this study, a prototype finger-temperature-detecting anti-counterfeiting label was prepared, and its temperature-response property was demonstrated.

Poly[(side-on mesogen)-alt-(end-on mesogen)]: A Compromised Molecular Arrangement

In recent years, sequence-controlled side-chain liquid crystal polymers (SCLCPs) have gained extensive interest because mesogenic units with different lengths and distributions can form various ord...

Synthesis and Characterization of Chiral azo LCPs

Precursor polymer MP series were synthesized by 4-allyloxybenzoic acid cholesteryl ester (M) and 4- hydroxyphenyl 4- (propionyloxy) benzoate (P). We obtained novel themotropic side-chain liquid crystal polymer MPZ series by esterification between MP series and 4-((4-ethoxyphenyl) diazenyl) benzoic acid (Z). Differential scanning calorimetry (DSC) was used to measure the thermal properties of those polymers, and the mesogenic properties were characterized by polarized optical micrograph (POM), DSC and X-Ray. MP series exhibited yellow, green, blue and purple Grandjean textures. MPZ series also showed colorful Grandjean textures. They exhibited thermotropic liquid crystal properties in a broad mesogenic region.