Synthesis of a liquid crystalline azobenzene monomer for photoalignment of ferroelectric liquid crystals

A liquid crystalline dimethacrylate-based monomer containing an azobenzene group was synthesized. The miscibility of the azo monomer and its crosslinked polymer network with ferroelectric liquid crystals (FLCs) was improved by the liquid crystallinity of the monomer. By performing thermal polymerization of the azo monomer dissolved in a FLC host under linearly polarized visible light irradiation, following a pre-irradiation with unpolarized UV light at room temperature, bulk alignment of the FLC could be induced in the absence of surface orientation layers, as a result of the photo-orientation of azobenzene moieties related to the reversible trans-cis photoisomerization of the chromophore. The optical and rubbing-free alignment of a FLC could be achieved with as few as 0.5 wt % of the azo polymer network. This represents a step toward the preparation of uniform samples of photoaligned FLC by reducing the amount of the azo polymer network that may be phase-separated from the FLC host.     

Photorefractive effect in composites of ferroelectric liquid crystal and photoconductive polymer

The photorefractive effect in composites of a ferroelectric liquid crystal (FLC) and several photoconductive polymers was investigated. The photorefractivity of mixtures of photoconductive polymers and an FLC (polymer/FLC), as well as that of photoconductive-polymer-stabilized ferroelectric liquid crystals (PPS-FLCs) was examined. The polymer/FLC samples exhibited two-beam coupling gain coefficients of about 6∼12 cm^-1 in a 5 µm gap cell. The photopolymerization of a methacrylate monomer in the FLC medium established a polymer-stabilized state in which the alignment of FLC molecules was mechanically stabilized. The noise in a two-beam coupling signal was reduced significantly in the PPS-FLC samples.     

Photorefractive effect in composites of ferroelectric liquid crystal and photoconductive polymer

The photorefractive effect in composites of a ferroelectric liquid crystal (FLC) and several photoconductive polymers was investigated. The photorefractivity of mixtures of photoconductive polymers and an FLC (polymer/FLC), as well as that of photoconductive‐polymer‐stabilized ferroelectric liquid crystals (PPS‐FLCs) was examined. The polymer/FLC samples exhibited two‐beam coupling gain coefficients of about 6～12 cm^?1 in a 5 µm gap cell. The photopolymerization of a methacrylate monomer in the FLC medium established a polymer‐stabilized state in which the alignment of FLC molecules was mechanically stabilized. The noise in a two‐beam coupling signal was reduced significantly in the PPS‐FLC samples.     

侧链含偶氮苯发色团的聚酰亚胺薄膜的制备及其三阶非线性光学和光存储性能的研究

将4,4'-二氨基三苯甲烷(DTM)单体与均苯四甲酸酐(PMDA)进行缩聚反应,再与对-硝基苯基重氮氟硼酸盐进行重氮偶合反应,然后经酰亚胺化合成了侧链含偶氮苯发色团的聚酰亚胺非线性光学材料(NLOPI).通过红外光谱对产物进行了结构表征.对产物的紫外-可见吸收光谱研究发现,在330和490nm处出现侧链偶氮苯发色团的特征吸收.通过简并四波混频方法(DFWM)测定侧链含偶氮苯发色团的聚酰亚胺薄膜的三阶非线性极化率χ⁽³⁾=4.58×10^-18m²/W.在DFWM中,前向泵浦光I_f和探测光I_p是主要的写入光,而后向泵浦光I_b是主要的读出光.证实了光致偶氮分子的顺反异构能够导致光信息存储的特性.     

A novel generation of photoactive comb‐shaped polyamides for the photoalignment of liquid crystals

A new approach to the synthesis of photoactive comb‐shaped homo‐ and copolyamides containing azobenzene, cinnamate, and coumarin side groups for photoalignment of liquid crystals was elaborated. Photooptical properties and photoorientational ability of these polymers with respect to liquid crystals were studied. It was shown that polarized UV irradiation of all spin‐coated polyamides leads to orientation of liquid crystalline molecules deposited on the polyamide thin films. The synthesized polymers containing cinnamate and coumarin side groups as well as azobenzene‐containing cyano‐ and nitro‐substituted polymers demonstrated good orientation ability in relation to liquid crystals displaying photoinduced planar orientation with high dichroism values within the range of 0.68–0.72. Contrary to the above‐mentioned polyamides, azobenzene‐containing fluorosubstituted polymers induced a homeotropic orientation of liquid crystals. It was shown that the synthesized photoactive polyamides can be considered as promising photoalignment materials for application in display technology, photonics, and other “smart” optical devices. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4031–4041     

Polymerization of polymer/ferroelectric liquid crystal composites formed with branched liquid crystalline bismethacrylates

Polymerization and phase behaviour of a branched liquid crystalline bismethacrylate in a ferroelectric liquid crystal (FLC) were characterized. Addition of the monomer increases the temperature range of the smectic A phase, and, at relatively low concentrations of monomer, the temperature range increases to more than 10 times that observed in the neat FLC. Other phases such as the smectic C* phase are no longer exhibited as the monomer interferes with the inherent tilt of the FLC molecules. After polymerization, the polymer network phase separates and the phase transition temperatures return to values close to those of the FLC. The monomer also shows a high degree of orientational order before polymerization, which is retained to a large extent after polymerization. The order in the polymer network results in considerable birefringence at temperatures well above the clearing point of the pure FLC. This behaviour is induced by the order of the polymer network and interactions of the FLC molecules with the network which prevent a fraction of the FLC molecules from exhibiting typical phase behaviour. In the formation of the branched liquid crystalline bismethacrylates/FLC composites, a steady increase is observed in the polymerization rate as the polymerization temperature increases and the order of the FLC phase decreases, a behaviour significantly different from that observed in other monomer/FLC mixtures for which the polymerization rate increases as the order of the FLC phase increases. Additionally, at appropriate polymerization temperatures around the clearing point, polymerization driven endothermic phase transitions may be observed.     

Preparation of photochromic polymers by stereospecific copolymerization of trans-4-(2-methacryloxyethyloxy)azobenzene and (−)-menthyl methacrylate

The synthesis is reported of a new photochromic monomer, trans-4-(2-methacryloxyethyloxy) azobenzene (MEAB), where the azobenzene chromophore is separated from the ester group by an ethylenoxy spacer arm. Comparative experiments show that trans-4-methacryloxyazobenzene (MAB), having the azobenzene group directly attached to the ester functionality, does not homopolymerize or copolymerize with (?)-menthyl methacrylate (MnMA) in the presence of different anionic initiators, whereas isotactic homopolymers and copolymers of MEAB can be obtained: the microstructure is described with reference to analogous atactic macromolecules.     

重氮偶合反应合成超支化偶氮聚合物的光响应性能研究

利用重氮偶合反应和后重氮偶合反应制备了主链和端基含有不同假芪型偶氮苯生色团的超支化偶氮聚合物.利用氢核磁共振、紫外光谱、红外光谱等分析手段确定了合成聚合物的结构、玻璃化转变温度和光谱特性等.研究了聚合物光致二向色性的性能,此聚合物的取向有序度为0.063.用两束相干的P偏振Ar+激光对聚合物膜进行光加工,得到形状规则的正弦波形表面起伏光栅,末端偶氮苯基团的引入极大地增加了超支化偶氮聚合物的光响应速度.     

Fluorescence and Photosensitizing Behavior of N-(p-Phenoxyphenyl)methacrylamide and Its Polymer

IntroductionWe have reported the syntheses of vinylmonomers bearing chromophores[1— 8] ,such as N -acryloyl- N′- 2 - pyrimidinylpiperazine,4- (N,N-dime- thylamino) benzyl methacrylate,N - acryloyl-N′- diphenylpiperazines,N- (4- dimethy-laminophenyl ) maleimide,N- (4- dimethy-laminophenyl) itaconimide,N- acryloylphenothiateetc.and their photochemical and photo- initiationbehaviors. Owing to the electron- donating chro-mophore and electron- accepting double bonds coex-isting in the same mo…     

Evolution of the switching current during the preparation of polymer network-ferroelectric liquid crystal microcomposites

The polymer network-ferroelectric liquid crystal (FLC) microcomposites are prepared by UV crosslinking of a chiral prepolymer diluted in a FLC. A fast cross-linking process involving 20 mW cm^-2 UV intensity produces material with ferroelectric properties which have strongly deteriorated compared with the pure FLC. By a slow process using a UV intensity of 2 mW cm^-2 the ferroelectric properties are less affected. It is supposed that the very dense polymer network, which arises during the fast process, is responsible for hindering the switching process and decreasing the spontaneous polarization. The photopolymerization kinetics are determined by measuring the switching current during the UV irradiation. The characteristic time of cross-linking is mainly reflected in the evolution of the spontaneous polarization and rotational viscosity with time.     

3-甲基丙烯酰胺基-9-乙基咔唑的合成、聚合及其光化学行为研究

含供电子芳杂环的丙烯酰类功能性单体的合成、聚合及光化学行为一直吸引着人们的兴趣 .原因之一是由于这类单体可用一般的自由基引发剂引发聚合 ,其聚合物表现出包括荧光及光引发行为的光化学性质甚被瞩目[1,2 ] .在以往的工作中发现 ,这类给电子性生色团的丙烯酰类单体在相同生色团浓度下的荧光强度明显低于其聚合物或饱和模型化合物 ,即表现出荧光结构自猝灭效应(ＳＳＱＥ) [3～ 5] .咔唑是一个强给电子性芳香杂环化合物 .虽然文献中已有关于含咔唑生色团的丙烯酰类单体报道 ,但很少涉及其荧光或光敏性质 .近来 ,我们合成了多个含有咔唑生…     

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.     

Photopolymerization kinetics of a thiol–enol composition determined via recording/playback of a transmission holographic diffraction grating

The kinetics of thiol–enol photopolymerization of a hybrid composition based on a tetraacrylate monomer and a thiol-siloxane oligomer was studied with the use of a holographic recording of elementary transmission phase gratings. The degrees of conversion of double bonds in the tetraacrylate monomer after the polymerization in air and in an inert atmosphere of SF₆ were measured via IR spectroscopy. It is shown that the use of the thiol-siloxane oligomer efficiently suppresses oxygen inhibition of the photopolymerization. When the photoinitiator concentration is increased to more than 10^–2 mol/L, the photopolymerization rate levels off. An increase in the thiol-siloxane oligomer concentration leads to an extremal dependence of the photopolymerization rate on the oligomer concentration; the maximum rate is reached at an oligomer concentration of about 0.07 mol/L. The kinetic scheme of photopolymerization in the hybrid photopolymer composition was analyzed, and an analytical expression for the photopolymerization rate was obtained. The correlation between the kinetic constants of the thiol–enol photopolymerization was evaluated on the basis of the obtained parameters of the kinetic model.     

Smectic layer structure of ferroelectric liquid crystal formed between fine polymer fibres

This paper describes the alignment of ferroelectric liquid crystal (FLC) structures formed between aligned polymer fibres, where the FLC smectic layers are determined by polarising microscopy and X-ray diffraction. The FLC/polymer composite films were formed from a nematic phase FLC/monomer solution using a photopolymerisation-induced phase separation method. It was found that bending of the FLC smectic layers was induced in both the film plane and the cross-sectional plane at the phase transition from smectic A to chiral smectic C of the FLC material. The light transmittance properties of the composite film between crossed polarizers was analysed by light propagation simulation in several optical anisotropic media, based on the evaluated smectic layer model.     

Smectic layer structure of ferroelectric liquid crystal formed between fine polymer fibres

This paper describes the alignment of ferroelectric liquid crystal (FLC) structures formed between aligned polymer fibres, where the FLC smectic layers are determined by polarising microscopy and X-ray diffraction. The FLC/polymer composite films were formed from a nematic phase FLC/monomer solution using a photopolymerisation-induced phase separation method. It was found that bending of the FLC smectic layers was induced in both the film plane and the cross-sectional plane at the phase transition from smectic A to chiral smectic C of the FLC material. The light transmittance properties of the composite film between crossed polarizers was analysed by light propagation simulation in several optical anisotropic media, based on the evaluated smectic layer model.     

Photoswitchable multivalent sugar ligands: synthesis, isomerization, and lectin binding studies of azobenzene-glycopyranoside derivatives

Coating of azobenzene chromophore with multivalent sugar ligands has been accomplished. Such sugar coating allows the study of the isomerization properties of this chromophore in aqueous solutions. The predominantly cis-isomer-containing photostationary state (PS) mixture of these azobenzene derivatives is found to be stable for hours. The rate constants for their isomerization, as well as the Arrhenius activation energies, are determined experimentally. An assessment of the lectin binding properties of the lactoside bearing isomeric azobenzene derivatives, by isothermal calorimetric methods, reveals the existence of an unusual cooperativity in their binding to lectin peanut agglutinin. Thermodynamic parameters evaluated for the trans and the PS mixture are discussed, in detail, for the lactoside bearing bivalent azobenzene derivative.     

PHOTORESPONSIVE ARTIFICIAL MEMBRANE. REGULATION OF MEMBRANE PERMEABILITY OF LIPOSOMAL MEMBRANE BY PHOTOREVERSIBLE CIS-TRANS ISOMERIZATION OF AZOBENZENES

Abstract— Photoresponsive artificial membranes have been prepared by embedding amphiphatic alkyl-ammonium salts containing azobenzene chromophore in dipalmitoylphosphatidylcholine liposomes. The configurational change due to trans→cis photoisomerization of the azobenzene chromophore provided the perturbation of the membrane structure to result in the increase of the water and bromo-thymol blue permeability of the liposomal membranes.     

含手性末端基偶氮聚合物膜的全息光栅研究

偶氮苯侧链型高分子由于其含有偶氮苯基团 ,在光作用下会发生可逆的顺反异构过程 ,具有光致取向特性 ,在光学处理、衍射光学、投影显示、光开关等许多方面具有潜在的应用性[1] .近 1 0多年来国内外学者对此类化合物进行了广泛的研究 ,已有文献报道可利用Ａｒ+激光束在偶氮苯聚合物薄膜上直接“写入”表面凸起光栅 ,并且通过原子力显微镜观测到光栅起伏 .这种光栅很稳定 ,并可以利用光学方法“擦去” .偶氮苯聚合物上述独有的性质引起了许多学者的兴趣[2 ,3] .另一方面 ,由于旋光性聚合物在光学物理性质上的优势 ,我们已将手性基团引入偶氮苯…     

Formation of a host nanostructure for ferroelectric liquid crystals using thiol-ene polymers

Liquid crystal displays are a subject of intense research interest because of their application to high definition display devices. Recently, polymer stabilized ferroelectric liquid crystals (PSFLCs) have been investigated due to the enhanced electro-optic properties of FLCs. We have utilized thiol-ene photopolymerizations to form a PSFLC system. Thiol-ene photopolymerizations are radical reactions, which proceed via a step growth reaction mechanism. During the polymerization, the polymer network structure is trapped into place due to the rapid transition from low molecular mass monomers and oligomers to high molecular mass polymer. This aspect is evidenced by phase transition data for the FLC, which indicates that the monomer and polymer are not phase separated from the FLC. Infrared dichroism shows that both monomer and polymer are ordered in parallel with the smectic layers of the FLC. Small angle X-ray scattering (SAXS) data show that both monomer and polymer are swelling the smectic layers. Thus, a polymer nanostructure is produced that serves as an ordered, stabilizing host for the FLC.     

Evolution of the switching current during the preparation of polymer network-ferroelectric liquid crystal microcomposites

The polymer network-ferroelectric liquid crystal (FLC) microcomposites are prepared by UV crosslinking of a chiral prepolymer diluted in a FLC. A fast cross-linking process involving 20 mW cm^-2 UV intensity produces material with ferroelectric properties which have strongly deteriorated compared with the pure FLC. By a slow process using a UV intensity of 2 mW cm^-2 the ferroelectric properties are less affected. It is supposed that the very dense polymer network, which arises during the fast process, is responsible for hindering the switching process and decreasing the spontaneous polarization. The photopolymerization kinetics are determined by measuring the switching current during the UV irradiation. The characteristic time of cross-linking is mainly reflected in the evolution of the spontaneous polarization and rotational viscosity with time.