Synthesis,photo-reaction and photo-induced liquid crystal alignment of soluble polyimide with pendant cinnamate group

In this paper, the synthesis, photo-reaction and photo-induced liquid crystal alignment of a polyimide with a pendant cinnamate group are reported. The polyimide was synthesized by the thermal imidization of the polyamic acid derived from 4,4'-(hexafluoro-isopropylidene)diphthalic anhydride and hydroxydiaminopropane, followed by the attachment of the cinnamate group to the main chain polyimide. The surface of thin layers of the polyimide was found to be preferentially occupied by the pendant cinnamate groups, and liquid crystal alignment on the polyimide thin film exposed to polarized UV was independent of the cinnamate content. The thermal stability of the photo-induced liquid crystal alignment was enhanced with decrease in the cinnamate content. This could be attributed to the strong interchain interaction of the polyimide chains which prevents thermal randomization of the photo-product of the pendant cinnamates. The dependences of the photo-reaction temperature and the annealing temperature of the alignment layer on the azimuthal anchoring energy of the photo-aligned liquid crystal suggest that the local stress developed during the UV irradiation profoundly influences the thermal stability of the liquid crystal alignment.     

Synthesis of photosensitive polyimide for liquid crystal alignment under non-polarised UV ageing lamp irradiation and a study on the possible mechanism of alignment

ABSTRACT

A new photosensitive polyimide (PI) was successfully synthesised via esterification of PI containing hydroxyl groups with cinnamoyl chloride (CL). The cinnamate (CA) group contents of the PI was up to 90%. The PI films could induce uniform parallel alignment of liquid crystal (LC) molecules after the non-polarised ultraviolet ageing lamp exposure, which reduce the cost significantly compared with polarised ultraviolet light equipment. In addition, the PI exhibited good thermal stability. Meanwhile, the possible mechanism of PI alignment films induced by NPUVL was discussed in some detail.     

Polyimides with main-chain photosensitive groups: Synthesis, characterization and their properties as liquid crystal alignment layers

In this work, a series of polyimides containing main-chain chalcone groups and side-chain cinnamate or acetate groups were synthesized. In the synthetic route, three dianhydride monomers were prepared by the reactions of 1,3-dihydro-1,3-dioxoisobenzofuran-5-carbonyl chloride with 1,3-bis(4-hydroxylphenyl)prop-2-en-1-one, 1,3-bis(4-(2-hydroxyethyl)phenyl)prop-2-en-1-one, and 1,3-bis(4-hydroxyphenyl)-pent-1-en-3-one-4-en, respectively. The precursor polyimides were obtained by the polycondensation of the dianhydride monomers with 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and the in situ imidization. After the polymerization, the final products were obtained by introducing the side groups through the reactions of the polyimide precursors with cinnamoyl chloride or acetic anhydride. The chemical structures and properties of the polyimides were characterized by elemental analysis, ¹H NMR, ¹³C NMR, FTIR, GPC, and thermal analysis. The polyimides show high thermal stability and good solubility in aprotic polar organic solvents. The polyimides can undergo sensitive [2+2] photocycloaddition reaction upon the UV light irradiation. After irradiation with linearly polarized UV light, the polyimide thin films can induce 5CB liquid crystal molecules to homogeneously align in the liquid crystal cells. Both the alignment ability and pretilt angles of the molecular orientation depend on the chemical structures of the polyimides.     

可溶性聚酰亚胺液晶取向膜的制备与性能

液晶取向膜是液晶显示器中的关键材料,为了制得性能优良的液晶取向膜,我们通过铃木偶联反应制备了3种含有不同末端基团的3,5-二氨基联苯,将制得的3种二胺单体分别与环丁烷四甲酸二酐聚合得到3种新型的聚酰亚胺。 利用核磁氢谱对单体和聚合物的结构进行了表征,测试了聚合物的溶解性、热稳定性以及用作液晶取向膜的性能。 结果表明,所得的聚酰亚胺具有良好的溶解性和热稳定性,经过机械摩擦后,末端带有甲氧基的聚酰亚胺能使液晶分子平行于摩擦方向取向,末端带有苯氧羰基和联苯氧羰基的聚酰亚胺能使液晶分子垂直于摩擦方向取向。 此类可溶性的聚酰亚胺液晶取向膜将简化制备工艺并在柔性显示器件中具有较大的应用价值。     

Polyimide-free homogeneous photoalignment induced by polymerisable liquid crystal containing cinnamate moiety

We designed and synthesised a reactive mesogen (CRM) containing cinnamate moiety in the core and two acrylate groups at both ends. The structure was characterised by ¹H NMR and FT-IR, and its liquid crystalline property was investigated by DSC and POM. The compound showed a nematic phase between 175.2 – 97.5 ^oC, followed by a smectic C phase between 97.5 and 57.9 ^oC during the cooling cycle. We proposed a fabrication method to achieve uniaxial homogeneous alignment of liquid crystals by irradiating the CRM-doped LC mixture in a sandwich cell of in-plane switching mode (CRM-IPS) with linearly polarised ultraviolet light. The results indicated that the CRM-IPS cell showed excellent initial dark state with a good alignment state, electro-optical performance and durability. This confirmed that the photo-induced alignment of LCs by CRM possesses outstanding alignment capability compared to the conventional rubbed polyimide alignment layer. We expect that this fabrication method is a promising candidate for cost-effective, green-manufacturing, and high-quality alignment method for the manufacturing of high-resolution liquid crystal displays (LCDs).     

Command surfaces 15 [1]. Photoregulation of liquid crystal alignment by cinnamoyl residues on a silica surface

The surface of a silica substrate plate was modified with a cinnamate moiety having a triethoxysilyl group at the ortho-position through a spacer. The plate was employed to assemble a cell filled with a nematic liquid crystal and exposed to linearly polarized 259 nm light to obtain homogeneous alignment. The direction of the alignment was perpendicular to an electric vector of the actinic light. On the contrary, the exposure of the cell to polarized light at 330 nm did not result in homogeneous alignment while the actinic light caused the disappearance of the chromophore. This wavelength effect on the azimuthal photoalignment suggests that the surface-assisted liquid crystal orientation is triggered by the reorientation of the E-isomer of the cinnamate group. This is in marked contrast to a proposed mechanism of a photoalignment by a thin film of a poly(vinyl cinnamate) derivative (Schadt et al., 1993, Jpn J. appl. Phys., 31, 2155); homogeneous alignment is induced by the axially selective photodimerization of cinnamate groups.     

Effect of photoreactivity of polyimide on the molecular orientation of liquid crystals on photoreactive polymer/polyimide blends

We prepared blend alignment layers from polymethacrylate with coumarin side chains (PMA-g-coumarin) and polyimides for the orientation of liquid crystals (LCs) using linearly polarized ultraviolet (UV) irradiation. We used two different polyimides, namely 4,4'-(hexafluoro-isopropylidene) diphthalic anhydride-3,5-diamino-benzoic acid (6FDA-DBA) and pyromellitic dianhydride-4,4'-oxydianiline (PMDA-ODA). It was found that the molecular orientation of the LC depended on the type of polyimide in the blend alignment layer. The thermal stability of the LC orientation was enhanced regardless of the type of polyimide, while the direction of LC orientation was different for each type of polyimide. The photoreactivity of the polyimide was a very important factor in determining the molecular orientation of the LC on the blend alignment layer. This may be attributed to the different mechanisms of LC orientation on PMA-g-coumarin and polyimide induced by the polarized UV irradiation. The direction of the LC orientation could be changed by controlling the photoreaction of the polyimides using the appropriate UV filter for the polarized UV irradiation.     

Study on polyvinylidene fluoride as alignment layer in twist-nematic liquid crystal display

The material with high dielectric constant can significantly affect the distribution of the electric field, so this kind of material has great potential in liquid crystal display. In this paper, polyvinylidene fluoride (PVDF) as alignment layer in liquid crystal display was analysed. The optical property, mechanical property, thermal stability and electrical property of PVDF were measured. Experiments show that the absorbance of PVDF material is 0.2 (or less) in visible light, which is better than the conventional alignment material polyimide (PI). The alignment effect can be generated by mechanical friction and the liquid crystal molecules are ordered or aligned, and PVDF can maintain good thermal stability as temperature is lower than 400°C. Since the dielectric constant of PVDF is usually between 6.0 and 8.0, it has significant effect on the distribution of the electric field in the liquid crystal display, and its dielectric loss is also less than PI. The lower operating voltage and the faster response time are obtained from the experiment. It can be confirmed by the experiments that PVDF could be used in liquid crystal display (LCD) as the alignment layer to improve LCD’s characteristics.     

Photo-induced liquid crystal alignment on polyimide containing fluorinated groups

Polyimides were prepared from pyromellitic dianhydride, 4,4'-bis[2-(4-aminophenyl)hexafluoroprop-2-yl]diphenyl ether and 4,4'-diamodiphenyl ether (PMDA-BDAF-ODA) and used for liquid crystal alignment using linearly polarized UV exposure. The alignment properties of a LC on the polyimide films were found to depend on the fluorine content in the PMDA-BDAF-ODA alignment layer and on the UV exposure time. Pretilt angles were obtained in the range 0° to 90° dependent upon the fluorine content in the polyimide film and the UV exposure time. These effects seem to be closely related to the surface energy of the photo-alignment layer.     

Bulk-mediated in-situ homogeneous photoalignment induced by reactive mesogen containing diphenylacetylene moiety

ABSTRACT

We designed and synthesised a reactive mesogen containing diphenylacetylene moiety in the mesogenic core and two polymerisable acrylate groups at both ends. By irradiating linearly polarised UV light on the conventional host LC mixture containing a small amount of the synthesised reactive mesogen in a sandwiched cell without an alignment layer, we demonstrated an in-situ photo-induced homogeneous alignment of liquid crystals without a pre-treated alignment layer, which was achieved by an irreversible polarisation-selective [2 + 2] photodimerization of diphenylacetylene moiety with linearly polarised UV irradiation at above the isotropic temperature of LC mixture. The resulting homogeneous alignment showed a superior initial dark state, negligible pretilt angle and excellent stabilities. Furthermore, the in-plane switching (IPS) LC cell prepared by this method exhibited a better dark state and electro-optic performance compared to that with conventional-rubbed polyimide alignment layer. The single photoirradiation process automatically resulted in a perfect alignment matching of optical axes between the top and bottom substrates in the LC cell, giving rise to an excellent dark state overcoming an intrinsic misalignment issue and complex fabrication process. The proposed in-situ alignment method is a promising candidate for cost-effective, green-manufacturing, and high-quality alignment technique in the manufacturing of high-resolution liquid crystal displays.     

Effect of photoreactivity of polyimide on the molecular orientation of liquid crystals on photoreactive polymer/polyimide blends

We prepared blend alignment layers from polymethacrylate with coumarin side chains (PMA-g-coumarin) and polyimides for the orientation of liquid crystals (LCs) using linearly polarized ultraviolet (UV) irradiation. We used two different polyimides, namely 4,4′-(hexafluoro-isopropylidene) diphthalic anhydride-3,5-diamino-benzoic acid (6FDA-DBA) and pyromellitic dianhydride-4,4′-oxydianiline (PMDA-ODA). It was found that the molecular orientation of the LC depended on the type of polyimide in the blend alignment layer. The thermal stability of the LC orientation was enhanced regardless of the type of polyimide, while the direction of LC orientation was different for each type of polyimide. The photoreactivity of the polyimide was a very important factor in determining the molecular orientation of the LC on the blend alignment layer. This may be attributed to the different mechanisms of LC orientation on PMA-g-coumarin and polyimide induced by the polarized UV irradiation. The direction of the LC orientation could be changed by controlling the photoreaction of the polyimides using the appropriate UV filter for the polarized UV irradiation.     

Thermal stability of alignment of a nematic liquid crystal induced by polyimides exposed to linearly polarized light

The thermal stability of alignment of a nematic liquid crystal (LC) on three polyimide (PI) films exposed to linearly polarized light at 366 nm was investigated. Polarizing optical microscopy analysis indicates that the thermal stability of the LC alignment on the PI film without significant structural change was higher than that with obvious structural change.     

Thermal stability of alignment of a nematic liquid crystal induced by polyimides exposed to linearly polarized light

The thermal stability of alignment of a nematic liquid crystal (LC) on three polyimide (PI) films exposed to linearly polarized light at 366 nm was investigated. Polarizing optical microscopy analysis indicates that the thermal stability of the LC alignment on the PI film without significant structural change was higher than that with obvious structural change.     

WHAT ARE THE DIFFERENCES OF POLYMER SURFACE RELAXATION FROM THE BULK?

The polymer surface relaxation in thin films has been a long debating issue.We report a new method on studying surface relaxation behaviors of polymer thin films on a solid substrate.This method involved utilizing a rubbed polyimide surface with a pretilting angle in a liquid crystalline cell.Due to the surface alignment,the liquid crystals were aligned along the rubbing direction.During heating the liquid crystalline cell,we continuously monitored the change of orientation of the liquid crystals.It is u...     

Molecular dynamics simulations of liquid crystal molecules on a polyimide monolayer

Preliminary results are presented on the molecular dynamics simulations of alignment of the liquid crystal molecule, 4-n-octyl-4'-cyanobiphenyl (8CB), on a polyimide (pyromelltic dianhydride-p-phenylene diamine) oligomer monolayer. We actually simulated a three-layer system, i.e., liquid crystal molecule/polyimide oligomer/a basal plane of graphite. First, simulations of the oligomers adsorbed on graphite were done in order to obtain reasonable adsorption structures, as the pre-stage simulation of the three-layer system. Then, by placing a liquid crystal layer on top, the three-layer system was simulated. The stable liquid crystal alignment direction on the polyimide monolayer was found roughly to be the polyimide chain direction with zero pretilt in this combination of liquid crystal and polymer materials. The calculated adsorption energy of an 8CB molecule to the polyimide monolayer was 128 kJ mol^-1 and the carbonyl group of the polyimide was the main adsorption site.     

Application of photosensitive polyimides as alignment layer to optical switching devices of a nematic liquid crystal

We have explored the change in alignment of a nematic liquid crystal, 4'-pentyl-4-cyanobiphenyl (5CB) with three types of photosensitive polyimide as the alignment layer by photoirradiation at 366 nm. The photosensitive polyimide alignment layer induced a reversible change in alignment of 5CB. It was observed that the 5CB molecules became aligned from homogeneous alignment to homeotropic on photoirradiation with a d.c. electric field as a bias, and reversed to the homogeneous state when photoirradiation was ceased. This result indicates that optical switching could be repeated by on and off switching of the excitation light at 366 nm. The optical switching of the nematic liquid crystal might be mainly due to a photophysical change in the polyimide surface which is affected by the chemical structures of the polyimides at the temperature at which 5CB exhibits a nematic phase. The optical switching of nematic liquid crystals with photosensitive polyimides as the alignment layer is a novel driving method for nematic liquid crystals.     

Application of photosensitive polyimides as alignment layer to optical switching devices of a nematic liquid crystal

We have explored the change in alignment of a nematic liquid crystal, 4'-pentyl-4-cyanobiphenyl (5CB) with three types of photosensitive polyimide as the alignment layer by photoirradiation at 366 nm. The photosensitive polyimide alignment layer induced a reversible change in alignment of 5CB. It was observed that the 5CB molecules became aligned from homogeneous alignment to homeotropic on photoirradiation with a d.c. electric field as a bias, and reversed to the homogeneous state when photoirradiation was ceased. This result indicates that optical switching could be repeated by on and off switching of the excitation light at 366 nm. The optical switching of the nematic liquid crystal might be mainly due to a photophysical change in the polyimide surface which is affected by the chemical structures of the polyimides at the temperature at which 5CB exhibits a nematic phase. The optical switching of nematic liquid crystals with photosensitive polyimides as the alignment layer is a novel driving method for nematic liquid crystals.     

Contrast ratio and switching of zigzag defect-free surface stabilized FLCD by photoinduced alignment

The contrast ratio and electro-optical switching behaviours of surface stabilized ferroelectric liquid crystal cells with alignment layers of a photodegradable polyimide prepared by polarized ultraviolet light irradiation have been investigated. The higher contrast ratio was obtained for a zigzag defect-free sample obtained by the photo-induced alignment method than by the rubbing method. The switching behaviours of the FLC, such as spontaneous polarization and response time, were measured. Higher spontaneous polarization and faster response times were obtained with cells prepared by the photoinduced alignment method. In addition, response times of the order of microseconds, which are fast enough to realize high quality moving images with video-frame rate, were obtained.     

Contrast ratio and switching of zigzag defect-free surface stabilized FLCD by photoinduced alignment

The contrast ratio and electro-optical switching behaviours of surface stabilized ferroelectric liquid crystal cells with alignment layers of a photodegradable polyimide prepared by polarized ultraviolet light irradiation have been investigated. The higher contrast ratio was obtained for a zigzag defect-free sample obtained by the photo-induced alignment method than by the rubbing method. The switching behaviours of the FLC, such as spontaneous polarization and response time, were measured. Higher spontaneous polarization and faster response times were obtained with cells prepared by the photoinduced alignment method. In addition, response times of the order of microseconds, which are fast enough to realize high quality moving images with video-frame rate, were obtained.     

光敏性聚酰亚胺的合成及其在液晶光致取向中的运用

通过羟基聚酰亚胺与肉桂酸的接枝反应合成了具有光敏性的聚酰亚胺,并且通过红外,核磁确定了光敏性聚酰亚胺的结构,将合成的聚酰亚胺作为液晶取向层用在液晶显示器件中,证明其有良好的热稳定性。