Broadband reflection in polymer stabilized cholesteric liquid crystal cells with chiral monomers derived from cholesterol

In this study, a series of achiral monomers and chiral monomers of different flexible spacer chains based on cholesteryl moiety were synthesized. Polymer stabilized cholesteric liquid crystal (PSCLC) cells were then created by incorporation of the polymer networks. The influence of the nature of the monomers and the spacer length of chiral monomers on the reflectance properties of PSCLC was investigated as well as the polymerization condition. The results strongly suggest that the chirality of the polymer networks plays an integral role in the observed reflection spectra, and the chiral polymer networks with chiral centers separated well from the polymer backbone induce a greater change in the bulk helix pitch, and produce the broader reflection band in these LC composites. In addition, the temperature dependence of the pitch of the composites before and after polymerization was investigated. To broaden the reflection band further, the experimental processes of thermally induced pitch variation simultaneously with a UV crosslinking reaction of the composites were presented. The morphology of the polymer network in the composites was studied by scanning electron microscopy (SEM). Copyright © 2008 John Wiley & Sons, Ltd.     

Interface modification of polymer stabilized cholesteric liquid crystal

Films were made by incorporating various quantities of fluoroalkyl acrylate (FA) into the chain termini of polyurethane acrylate oligomer of polymer stabilized cholesteric liquid crystals (PSCLCs). The effects of switching voltage, scanning electron and polarized optical microscope morphologies, texture transition and reversibility, and contact angle of the films were then studied. It was found that the switching voltage of the film decreased with the addition of FA up to 0.8 wt%, beyond which it increased. The decrease and increase were respectively explained in terms of decreased interface energy as noted from the contact angle of the LC on polymer surface, and too small droplet size as noted from the SEM. Copyright © 2008 John Wiley & Sons, Ltd.     

New chiral liquid crystal monomers and cholesteric polyacrylates: synthesis and characterisation

The synthesis of new chiral monomers (M₁ ?M₃ ) based on menthol and the corresponding polyacrylates (P₁ ?P₃ ) is described. The chemical structures, formula and phase behaviour of the obtained monomers and polymers were characterised with FT-IR, ¹H-NMR, elemental analyses, differential scanning calorimetry (DSC), polarising optical microscopy (POM) and X-ray diffraction (XRD). The effect of the mesogenic core rigidity, spacer length and menthyl steric effect on the phase behaviour of M₁ ?M₃ and P₁ ?P₃ is discussed. The expected mesophase of the compounds based on menthol can be obtained by inserting a flexible spacer between the mesogenic core and the terminal groups. For the chiral monomers and polyacrylates, their corresponding melting temperature (T _m), glass transition temperature (T _g) and clearing temperature (T _i) increased with an increase of the mesogenic core rigidity; while the T _m, T _g and T _i decreased with increasing the spacer length. M₁ and P₁ showed no mesophase, while M₂ and M₃ all revealed a SmC* and cholesteric phases. P₂ and P₃ only showed a cholesteric phase.     

Effect of specific rotation of chiral dopant and polymerization temperature on reflectance properties of polymer stabilized cholesteric liquid crystal cells

A series of polymer stabilized cholesteric liquid crystal (PSCLC) cells were prepared by photo‐polymerization of a cholesteric liquid crystal (Ch‐LC) mixture containing a nonreactive LC, a nematic diacrylate and a novel cholesteryl monomer. The influence of the specific rotation and concentration of the chiral dopants, and the polymerization temperature on reflection properties was investigated. The results demonstrate that the reflection band was broadened after polymerization for all the systems both left‐handed S811 and right‐handed R1011 as the chiral dopant, which is speculated to be a result of an inhomogeneous consumption of the chiral monomer within the system. Additionally, the polymer temperature plays an integral role in the observed reflection spectra, and at optimum polymerization temperature the broadband reflection effect becomes much more pronounced. Scanning electron microscopy (SEM) was used to examine the role of microscopic changes of the polymer network induced by polymerization temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1562–1570, 2008     

Optical behaviour of cholesteric liquid crystal cells with novel photoisomerizable chiral dopants

In order to investigate the effect of photoisomerization of E–Z structures on the optical behaviour of cholesteric liquid crystal (ChLC) cells, a series of novel azo derivatives was synthesized. Molecular structures were identified using ¹H NMR, ¹³C NMR, FTIR and elemental analysis. Thermal properties and the specific rotation of the synthesized chiral azo derivatives were estimated. Rubbed polyvinyl alcohol coated on the inner surface of substrates was used to control the liquid crystal alignment in cells. The effect of chiral dopants on the reflection band of ChLC cells was investigated, as well as the dependence of polarizing optical microscope textures on temperature. The stability and reproducibility of the effect of UV irradiation on the cell reflection band and real image recording were confirmed. Real image recording of the ChLC cells fabricated in this investigation was also studied; a photoinduced image through a mask is given. Photoirradiated and non‐irradiated areas appear as different reflected colours leading to the formation of an image. Stacking of the ChLC cells was found to intensify the brightness of the reflection band.     

Optical behaviour of cholesteric liquid crystal cells with novel photoisomerizable chiral dopants

In order to investigate the effect of photoisomerization of E-Z structures on the optical behaviour of cholesteric liquid crystal (ChLC) cells, a series of novel azo derivatives was synthesized. Molecular structures were identified using ¹H NMR, ¹³C NMR, FTIR and elemental analysis. Thermal properties and the specific rotation of the synthesized chiral azo derivatives were estimated. Rubbed polyvinyl alcohol coated on the inner surface of substrates was used to control the liquid crystal alignment in cells. The effect of chiral dopants on the reflection band of ChLC cells was investigated, as well as the dependence of polarizing optical microscope textures on temperature. The stability and reproducibility of the effect of UV irradiation on the cell reflection band and real image recording were confirmed. Real image recording of the ChLC cells fabricated in this investigation was also studied; a photoinduced image through a mask is given. Photoirradiated and non-irradiated areas appear as different reflected colours leading to the formation of an image. Stacking of the ChLC cells was found to intensify the brightness of the reflection band.     

Optical behaviour of photoimageable cholesteric liquid crystal cells with various novel chiral compounds

In theory, both polarity and steric hindrance are basic factors which affect molecular interactions. To investigate the optical properties and steric structures of chiral compounds having different chiral moieties which affect the wavelength of light reflection in liquid crystal (LC) cells, a series of novel chiral compounds and azobenzene derivatives were synthesized. The liquid crystalline phases of the compounds were identified using small angle X-ray diffraction, differential scanning calorimetry and polarizing optical microscopy. Cholesteric LC cells with various synthesized chiral dopants which selectively reflect visible light were first prepared, the photochemical switching behaviour of colours was then investigated, with special reference to the change in transmittance in cholesteric LC cells containing an azobenzene derivative as a photoisomerizable guest molecule. Reversible isomerization of azobenzene molecules occurred in the cholesteric systems, resulting in a depression of T_ChI and a shift of the selectively reflected wavelength. We discuss the photochemically driven change in the helical pitch of the cholesteric LCs with respect to structural effects involving the chiral moieties. Molecular interactions caused by the added dopants, reliability and stability of the photoisomerization, and UV irradiation effects on the cholesteric LC cells were also investigated. A real image was recorded through a mask on a cholesteric LC cell fabricated in this investigation.     

Optical behaviour of photoimageable cholesteric liquid crystal cells with various novel chiral compounds

In theory, both polarity and steric hindrance are basic factors which affect molecular interactions. To investigate the optical properties and steric structures of chiral compounds having different chiral moieties which affect the wavelength of light reflection in liquid crystal (LC) cells, a series of novel chiral compounds and azobenzene derivatives were synthesized. The liquid crystalline phases of the compounds were identified using small angle X‐ray diffraction, differential scanning calorimetry and polarizing optical microscopy. Cholesteric LC cells with various synthesized chiral dopants which selectively reflect visible light were first prepared, the photochemical switching behaviour of colours was then investigated, with special reference to the change in transmittance in cholesteric LC cells containing an azobenzene derivative as a photoisomerizable guest molecule. Reversible isomerization of azobenzene molecules occurred in the cholesteric systems, resulting in a depression of T _ChI and a shift of the selectively reflected wavelength. We discuss the photochemically driven change in the helical pitch of the cholesteric LCs with respect to structural effects involving the chiral moieties. Molecular interactions caused by the added dopants, reliability and stability of the photoisomerization, and UV irradiation effects on the cholesteric LC cells were also investigated. A real image was recorded through a mask on a cholesteric LC cell fabricated in this investigation.     

Time‐dependent deformation of structurally chiral polymer networks in stabilized cholesteric liquid crystals

Polymerization of crosslinkable liquid crystal monomers in chiral liquid crystalline media stabilizes the phase and enables distinct electro‐optic properties relative to small‐molecule analogs. Particularly interesting are cases where the polymerization forms a crosslinked polymer network that maintains a “structural” chirality. Recent reports have employed this methodology to realize a diverse set of electro‐optic responses in polymer stabilized cholesteric liquid crystals (PSCLCs) including reflection bandwidth broadening, reflection wavelength tuning, and dynamic scattering modes. It has been proposed that the mechanism at the root of these electro‐optic responses is an ion‐mediated, electromechanical deformation of the stabilizing and structurally chiral polymer network. In an effort to better understand the nature of these deformations, here we have characterized the electro‐optic response of PSCLCs with different polymer concentrations and crosslink densities. The dynamic response of PSCLCs to electric fields exhibits a time‐dependent behavior reminiscent of the creep of polymeric materials to mechanical deformations. The electro‐optic response can be described as the superposition of two contributions: the fast deformation of a relatively soft component of the polymer network (1–2 s) and the slower (10–20 s) deformation of a harder component. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1087–1093     

Synthesis and characterization of side chain cholesteric liquid crystalline elastomers derived from chiral bisolefinic crosslinking units

In this work we prepared a nematic monomer (4′‐allyloxybiphenyl 4′‐ethoxybenzoate, M₁ ), a chiral crosslinking agent (isosorbide 4‐allyloxybenzoyl bisate, M₂ ) and a series of new side chain cholesteric liquid crystalline elastomers derived from M₁ and M₂ . The chemical structures of the monomers and polymers were confirmed by FTIR and ¹H NMR spectroscopy. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X‐ray diffraction. The effect of the content of the crosslinking unit on phase behaviour of the elastomers is discussed. Polymer P₁ showed a nematic phase, P₂ –P₇ showed a cholesteric phase; P₆ formed a blue Grandjean texture over a broad temperature range 145–209.6°C, with no changed on the cooling. Polymers P₄ –P₇ , with more than 6?mol?% of chiral crosslinking agent, gave rise to selective reflection. Elastomers containing less than 15?mol?% of the crosslinking units displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. Experimental results demonstrated that, with increasing content of crosslinking agent, the glass transition temperatures first fell and then increased; the isotropization temperatures and mesophase temperature ranges decreased.     

Synthesis and characterization of side chain cholesteric liquid crystalline elastomers derived from chiral bisolefinic crosslinking units

In this work we prepared a nematic monomer (4'-allyloxybiphenyl 4'-ethoxybenzoate, M₁), a chiral crosslinking agent (isosorbide 4-allyloxybenzoyl bisate, M₂) and a series of new side chain cholesteric liquid crystalline elastomers derived from M₁ and M₂. The chemical structures of the monomers and polymers were confirmed by FTIR and ¹H NMR spectroscopy. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X-ray diffraction. The effect of the content of the crosslinking unit on phase behaviour of the elastomers is discussed. Polymer P₁ showed a nematic phase, P₂-P₇ showed a cholesteric phase; P₆ formed a blue Grandjean texture over a broad temperature range 145-209.6°C, with no changed on the cooling. Polymers P₄-P₇, with more than 6 mol % of chiral crosslinking agent, gave rise to selective reflection. Elastomers containing less than 15 mol % of the crosslinking units displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. Experimental results demonstrated that, with increasing content of crosslinking agent, the glass transition temperatures first fell and then increased; the isotropization temperatures and mesophase temperature ranges decreased.     

Dye induced great enhancement of broadband reflection from polymer stabilized cholesteric liquid crystals

A series of polymer stabilized cholesteric liquid crystals (PSCLCs) films were prepared from cholesteric liquid crystal (Ch‐LC) mixtures containing different components such as non‐reactive LC monomer, polymerizable monomer, chiral dopant, dye, and photoinitiator upon polymerization. The influence of the polymerizable monomer and dye of Ch‐LC mixtures on the reflection properties was investigated. The reflection bandwidth for all the samples can be increased by photo‐polymerization, and the network upon polymerization derived from two different polymerizable monomers with both one and two functional groups is more effective than that from one polymerizable monomer for broadening the reflection band. Especially, a dye‐doped Ch‐LC film can reflect incident light with the bandwidth over the wavelength range of 550–2350 nm, which is due to a greater pitch gradient formed inside of Ch‐LC film. The gradient pitch network structure was firstly demonstrated by scanning electron microscopy (SEM) with the film prepared from high diacrylate monomer concentration and subsequently proved by using a wash‐out/refill method. The nematic liquid crystals monomers was infiltrated into the polymer network that was prefabricated by removing the low molar weight LCs from the original PSCLCs film, and SEM exhibited the existence of a pitch gradient across the film thickness. The refilled nematic liquid crystals film showed broadband reflection after polymerzition, too. Copyright © 2011 John Wiley & Sons, Ltd.     

Photochemical tuning capability of cholesteric liquid crystal cells containing chiral dopants end capped with menthyl groups

In order to investigate the photochemical tuning capability of chiral monomers and polymers containing end-capped menthyl groups, a new series of chiral dopants was synthesized and added to commercially available nematic liquid crystals to induce cholesteric liquid crystal (LC) phases. The addition of chiral dopants with azo structure led to phototunability of the reflection colour of the LC cells. Photochromic variation of the LC cells due to photoisomerization of the azo compound was investigated. After photopolymerization of the monomers inside the cholesteric LC cells, the centre wavelength of the reflected band of the incident light was found to be fixed and the reflected bandwidth was broadened, resulting in a red shift. A schematic representation of both the photoisomerization of the azo dopants and its effect on variation of twisting pitches is proposed. Real image recording was performed using 365 nm UV through a mask with text. The top and side views of the morphological network structures of a fabricated cholesteric LC cell were investigated using scanning electron microscopy. The results of this investigation demonstrated that RGB reflected colours of LC cells can easily be achieved through the addition of the menthyl-containing synthesized chiral compounds to nematic LCs. The addition of synthesized AzoM helped further in recording the patterns onto cholesteric LC films using 365 nm UV exposure.     

Photochemical tuning capability of cholesteric liquid crystal cells containing chiral dopants end capped with menthyl groups

In order to investigate the photochemical tuning capability of chiral monomers and polymers containing end‐capped menthyl groups, a new series of chiral dopants was synthesized and added to commercially available nematic liquid crystals to induce cholesteric liquid crystal (LC) phases. The addition of chiral dopants with azo structure led to phototunability of the reflection colour of the LC cells. Photochromic variation of the LC cells due to photoisomerization of the azo compound was investigated. After photopolymerization of the monomers inside the cholesteric LC cells, the centre wavelength of the reflected band of the incident light was found to be fixed and the reflected bandwidth was broadened, resulting in a red shift. A schematic representation of both the photoisomerization of the azo dopants and its effect on variation of twisting pitches is proposed. Real image recording was performed using 365 nm UV through a mask with text. The top and side views of the morphological network structures of a fabricated cholesteric LC cell were investigated using scanning electron microscopy. The results of this investigation demonstrated that RGB reflected colours of LC cells can easily be achieved through the addition of the menthyl‐containing synthesized chiral compounds to nematic LCs. The addition of synthesized AzoM helped further in recording the patterns onto cholesteric LC films using 365 nm UV exposure.     

Polymer modified and stabilized cholesteric liquid crystal materials for flat panel application

Polymer dispersions, even in very low concentrations, can improve the performance of cholesteric liquid crystal materials necessary for their application in flat panel displays. Normal scattering mode, reverse scattering mode and reflective mode cholesteric liquid crystal materials are described. The roll of the polymer in each of these display modes is reviewed as are the unique electro-optic characteristics of the dispersions.     

Generation mechanism of residual direct current voltage for liquid crystal cells with polymer layers produced from monomers

Liquid crystal cells having polymer layers produced from copolymers of 4,4′-dimethacryloyl-oxy-biphenyl (4,4′-DMABiph) and anthracene-carrying monomers, 2,7-dimethacryloyl-oxy-anthracene (2,7-DMAAnth) and 2-methacryloyl-oxy-anthracene (2-MAAnth), were fabricated, and generation mechanism of residual direct current voltage (V_rDC) was clarified. The V_rDC was improved with the LC cells having the polymer layers produced from the copolymers of 4,4′-DMABiph and 2,7-DMAAnth due to large rate constant of polymerisation. In contrast, the V_rDC was increased with the LC cells having the polymer layers produced from the copolymer of 4,4′-DMABiph and 2-MAAnth. The increase in the V_rDC was derived from the increase in the concentration of polymerised- or unpolymerised-terminally radical and ion generated from 2-MAAnth. The results suggest that the monomers should show large rate constant of polymerisation with plural number of polymerised groups for improving the V_rDC.     

Polymer-stabilized cholesteric liquid crystal microgratings: a comparison of polymer network formation and electro-optic properties for mesogenic and non-mesogenic monomers

Polymer-stabilized liquid crystal microgratings are made using a focused Gaussian UV laser beam to photopolymerize 3 wt % reactive monomer in a cholesteric liquid crystal host. In a typical case, round gratings of 300 μm diameter and 10 μm pitch are produced. The microgratings highlight interesting differences between mesogenic and non-mesogenic monomers in the assembly and spatial distribution of polymer networks formed in a cholesteric host. We also observe a corresponding variation in the electro-optical properties of the stabilized gratings. In the mesogenic case, the grating state of the liquid crystal is faithfully captured even for relatively short UV exposures and over regions only a few pitch lengths in size. These findings are consistent with phase separation of the mesogenic monomer into regular domains templated by periodic, macroscopic variations in orientational order of the host. This templating effect is significantly reduced in the non-mesogenic case.     

Polymer-stabilized cholesteric liquid crystal microgratings: a comparison of polymer network formation and electro-optic properties for mesogenic and non-mesogenic monomers

Polymer-stabilized liquid crystal microgratings are made using a focused Gaussian UV laser beam to photopolymerize 3 wt % reactive monomer in a cholesteric liquid crystal host. In a typical case, round gratings of 300 μm diameter and 10 μm pitch are produced. The microgratings highlight interesting differences between mesogenic and non-mesogenic monomers in the assembly and spatial distribution of polymer networks formed in a cholesteric host. We also observe a corresponding variation in the electro-optical properties of the stabilized gratings. In the mesogenic case, the grating state of the liquid crystal is faithfully captured even for relatively short UV exposures and over regions only a few pitch lengths in size. These findings are consistent with phase separation of the mesogenic monomer into regular domains templated by periodic, macroscopic variations in orientational order of the host. This templating effect is significantly reduced in the non-mesogenic case.     

Improvement of image sticking on liquid crystal displays with polymer layers produced from mixed monomers

As a model of polymer-sustained-alignment liquid crystal display (PSA-LCD), the LC cells having the polymer layers produced from the homopolymers and copolymers of 4,4?-dimethacryloyl-oxy-biphenyl (4,4?-DMABiph) and 2,6-dimethacryloyl-oxy-naphthalene (2,6-DMANaph) were prepared and investigated image sticking phenomenon with evaluations of residual direct current voltage (V_rDC) and difference in pre-tilt angle before and after application of alternate current (AC) voltage (Δtilt). The V_rDC was effectively improved by adding a small amount of 2,6-DMANaph to 4,4?-DMABiph because the concentrations of radicals and ions in the LC layer were decreased due to increase in the rate constant of the polymerisation with the addition of 2,6-DMANaph under UV light exposure. The Δtilt was proportionally increased with increasing the weight ratio of 2,6-DMANaph in the mixed monomers of 4,4?-DMABiph and 2,6-DMANaph. We confirmed that the range of the weight ratio for 2,6-DMANaph in the mixed monomers of 4,4?-DMABiph and 2,6-DMANaph from 10 to 25 wt% was useful for obtaining the small level of image sticking in the PSA-LCD.