纤维素胆甾型液晶研究进展

主要介绍了近年来在纤维素胆甾型液晶领域的研究进展,包括其制备：形成机理、织构特性及其影响因素等方面。     

Achiral Dichroic Dyes-mediated Circularly Polarized Emission Regulated by Orientational Order Parameter through Cholesteric Liquid Crystals

It is noteworthy that cholesteric liquid crystal (CLC) platforms have been witnessed in high-performance circularly polarized luminescence (CPL) behaviors through the highly organized chiral co-assembled arrangement of achiral dyes. However, most CPL-active design strategies are closely relative to the helix co-assembly structure of CLC rather than achiral dyes. Herein, we developed an intriguing regulation strategy for CPL-active CLC materials. They were regulated using the orientational order parameter (S_F) of achiral dichroic dyes as an incisive probe for the order arrangement degree of achiral dyes in CLC media. The I-shaped phenothiazine derivative PHECN dye (S_F=0.30) emitted a strong CPL signal (|g_lum|=0.47). In contrast, the T-shaped derivative (PHEBen) dye (S_F=0.09) showed a weak circular polarization level (|g_lum|=0.07) at similar CLC textures. Most interestingly, this kind of dichroic PHECN dye with a higher S_F could greatly improve the contrast ratio of CPL (Δg_lum=0.47) and emission intensity (ΔFL=46.0 %) at direct-current electric field compared with the T-shaped PHEBen (Δg_lum=0.07 and ΔFL=1.0 %) in CLC. This work demonstrates that an induced CPL emission can be mediated using achiral dichroic dye, which will open a new avenue for developing excellent CPL-active display materials.     

Effect of Blending of Cholesteric Cellulose Esters on the Pitch Height

Butyric esters (BuPC) of hydroxypropylcellulose (HPC) with different degrees of substitution (DS) were obtained by the reaction of (2‐hydroxypropyl)cellulose with butyryl chloride. Blends of these BuPCs were obtained from ternary solutions by removal of the common solvent. The blends displayed thermotropic cholesteric mesophases and showed iridescent colors at ambient temperatures depending on the blend composition. The spectroscopic analysis of the blends showed systematic variations of the reflection colors with variations of the ratio of the blend components between the reflection colors of the pure blend components covering the range from 453–938 nm corresponding to pitch heights from 308–640 nm.     

Cholesteric bonded stationary phases for high-performance liquid chromatography: a comparative study of the chromatographic behavior

The properties of four cholesteric bonded stationary phases differing in the nature of the spacer and the end-capping were assessed using simple chromatographic tests based on the retention of nonpolar compounds and of planar or nonplanar probe solutes. All cholesteric columns showed a hydrophobicity close to that of conventional octadecyldimethylsilyl (ODS) materials. Non-end-capped cholesteric bonded phases showed greater selectivity than ODS ones and both end-capped cholesteric bonded phases exhibit behavior intermediate between that of the non-end-capped original material and that of the ODS bonded phase.     

2,2'-二苯并噁唑衍生物的合成和光性能研究

合成了16种2,2-二苯并(口恶)唑衍生物,测定了化合物的熔点、红外光谱、紫外吸收光谱、荧光发射光谱以及荧光量子产率,与1,4-二(苯并(口恶)唑1′,3′-基-2′)苯和1,4-二(苯并(口恶)唑-1′,3′-基-2′)乙烯衍生物进行了比较,讨论了它们之间光谱特性的差异.     

Structure and Transport Properties of Films of Mixed Cellulose Esters

Cellulose acetomyristates of varied composition were studied. The sample volume abnormally increases in high-temperature stretching and after swelling in benzene. Cellulose acetomyristates can be used as membranes for separating aromatic and aliphatic hydrocarbons.     

Synthesis of phosphorus dendrimers bearing chromophoric end groups: toward organic blue light-emitting diodes

Several series of phosphorus dendrimers decorated by potential fluorescent end groups (naphthalene, anthracene, and pyrene) have been synthesized. Unexpectedly, we found that it is absolutely necessary to link the fluorophore to the dendrimer through an alkyl link, and not directly through heteroelements such as oxygen or nitrogen, in order to preserve the fluorescence. One series of dendrimers from generation 1 (6 pyrene end groups) to generation 4 (48 pyrene end groups) has been tested for the elaboration of organic light-emitting diodes (OLEDs). The threshold voltage for the emission of light is high (over 20 V), however, electroluminescence is observed in all cases.     

Synthesis, structure and mesomorphism of new cholesteric monomers and smectic comblike polymers

Seven new cholesteric monomers (M-1−M-7) and the corresponding smectic comblike polymers containing cholesteryl groups (P-1−P-7) were synthesized. The chemical structures and purity were characterized by FT-IR, ¹H NMR, and elemental analyses. The specific optical rotations were evaluated with a polarimeter. The mesomorphism was investigated by polarizing optical microscopy, differential scanning calorimetry, thermogravimetric analysis, and X-ray diffraction. The specific optical rotation values of these monomers and polymers with the same numbers of phenyl ring and terminal groups were nearly equal, however, they decreased with increasing the aryl numbers in the mesogenic core. M-1−M-7 showed oily streak texture and focal conic texture, or fingerprint texture, or spiral texture of cholesteric phase. P-1−P-7 showed the smectic A phase. The melting, clearing, and glass transition temperatures increased, and the mesophase temperature ranges widened with increasing the aryl number in the mesogenic core. Surprisingly, although the molecular structures of M-6 and M-7 were similar to those of M-4, namely the mesogenic cores contained three phenyl rings, their phase behavior had a considerable difference, and T_m and T_i of M-6 and M-7 were less than those of M-4. In addition, M-6 and M-7 also showed an obvious glass transition. TGA showed that all the polymers had good thermal stabilities.     

Synthesis and characterization of new cholesteric monomers and smectic polymers containing menthyl groups

New cholesteric monomers (M₂−M₅) and the corresponding smectic homopolymers (P₂−P₅) based on menthyl groups were synthesized. The chemical structures were characterized by Fourier transform infrared and ¹H NMR. The specific optical rotations were evaluated with a polarimeter. The structure–property relationships of the new compounds are discussed. The mesomorphism was investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction. The selective reflection property of light was studied with UV/Visible/NIR. The monomers M₂−M₅ formed the cholesteric or blue phase when a flexible link chain was inserted between the mesogenic core and the terminal menthyl groups by reducing the steric effect. M₁ showed no mesomorphism, while M₂−M₅ revealed enantiotropic cholesteric phase. In addition, M₂ and M₃ also showed a cubic blue phase on cooling. The selective reflection of light for M₂−M₅ shifted to the short reciprocal wavelength region with increasing the temperature or intramolecular spacer length. P₂−P₅ exhibited the smectic A phase. The melting, clearing, and glass transition temperatures increased when increasing the aryl number in the mesogenic core or decreasing the intramolecular spacer length.     

Synthesis,Characterization, and Thermotropic Properties of Liquid Crystals with an Oligo (Ethylene Oxide) Monomethyl Substituent I: Biphenyl-Based Systems

New alkene liquid crystals 4-[oligo(ethylene oxide)_o, monomethylether)carbonyl]phenyl 4-[4(allyloxy) phenyl]benzoate(MBPBEn, n = 1-3), 4′-[oligo(ethylene oxide)_o, monomethylether)carbonyl]biphenyl-4-yl 4-[4-(al1yloxy)phenyl]benzoate(MBPBPEn, n = 1-3), (S)-4-[(2-methyl-I-butoxy)carbonyl]phenyl 4[4-(allyloxy)phenyl]benzoate(MBPBKA), and (S)-4′-[(2-methyl-l-butoxy)carbonyl]biphenyl-4-yl 4-[4(allyloxy)phenyl]benzoate(MBPBPKA) were synthesized and characterized using ¹H-NMR and elemental analysis methods. The thermal transition temperatures, mesomorphic properties, and mesophase textures of these compounds have been determined by differential scanning calorimetry (DSC), by polarizing optical microscopy, and by X-ray diffraction analysis. The effect of changes in chemical structure on the mesophase properties, mesophase and isotropic transition temperatures, and mesophase textures are discussed.     

Synthesis and characterization of side-chain cholesteric elastomers derived from an isosorbide crosslinking agent

New liquid crystalline monomer 4-(4-ethoxybenzoyloxy)biphenyl-4′-[(10-undecylen-1-yloxy)-4′-ethoxy]benzoate (M ₁ ), chiral crosslinking agent isosorbide di-(10-undecylen-1-yloxybenzoate) (M ₂ ), and the corresponding elastomers were prepared. The chemical structures of M ₁ and M ₂ were characterized by Fourier transform infrared and ¹H-nuclear magnetic resonance. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction measurements. M ₁ exhibited typical threaded texture and droplet texture of nematic phase. The use of chiral crosslinking agent in the polymer networks could induce cholesteric phase. The elastomers containing less than 10 mol% of the chiral crosslinking units showed elasticity, reversible phase transition, wide mesophase temperature ranges, and high thermal stability. For the elastomers P ₂ –P ₄ , the glass transition temperature (T _g) increased; clearing temperature (T _i) and mesophase temperature range (ΔT) decreased with increasing content of the crosslinking unit.     

含有萘并噻二唑的红光电致发光聚合物的合成和性能研究

以2,7-二溴-9,9-双(N,N-二甲基丙胺基)芴与4,7-双(5-溴-2-噻吩)-2,1,3-萘并噻二唑为共聚单体, 通过Suzuki偶合反应合成按不同比例共聚的一系列共轭聚合物, 并对它们的电致发光性能进行了研究. 结果表明, 所有的聚合物均在高功函数金属铝作阴极的器件中具有较高的发光效率, 最大电致发光外量子效率为1.3%, 好于目前广泛应用的低功函数金属(如钡, 钙等)作阴极的发光效率.     

Side-chain cholesteric liquid crystalline elastomers derived from a mesogenic crosslinking agent: I. Synthesis and mesomorphic properties

The synthesis of new side-chain cholesteric elastomers derived from a cholesteric monomer and mesogenic crosslinking agent is presented. The chemical structures of the monomers obtained were confirmed by elemental analyses, FT-IR, ¹H NMR, and ¹³C NMR. The mesomorphic properties and thermal stability were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), polarizing optical microscopy (POM), and X-ray diffraction (XRD) measurements. M₁ showed cholesteric phase, and M₂ displayed enantiotropic nematic phase and monotropic smectic phase. The elastomers containing less than 12 mol% of the crosslinking units revealed reversible mesomorphic phase transition, wide mesophase temperature ranges, and high thermal stability.     

Synthesis and properties of new chiral mesogenic monomers and side-chain smectic homopolymers containing (−)-menthyl groups

The synthesis of new chiral monomers (M₁−M₅) and the corresponding smectic homopolymers (P₁−P₅) containing menthyl groups is described. The chemical structures and purity were characterized by FT-IR, ¹H NMR and elemental analyses. The specific optical rotations were evaluated with a polarimeter. The phase behavior and mesomorphism were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction. The selective reflection property of light was studied with UV/visible/NIR. The monomers M₂−M₅ formed a chiral smectic C , and cholesteric or blue phase when a flexible linkage chain was inserted between the mesogenic core and the terminal menthyl groups by reducing the steric effect. M₁ showed no mesomorphism, while M₂−M₅ showed enantiotropic and cholesteric phases. Moreover, M₅ also exhibited a cubic blue phase on cooling. With increasing temperature, the selective reflection of light shifted to the long wavelength region at the phase range, and to the short wavelength region at the cholesteric phase range, respectively. The homopolymers P₁−P₅ all exhibited the batonnet textures of a smectic A phase. The melting, clearing, and glass transition temperatures increased, and the mesophase temperature ranges widened with increasing the aryl number in the mesogenic core.     

三苯甲酰基纤维素酯微珠的制备

以微晶纤维素为原料合成三苯甲酰基纤维素酯，将粉末状的三苯甲酰基纤维素酯转变成用于高效液相色谱手性填料的微珠，通过扫描电子显微分析考察了微珠的粒径分布。     

Synthesis and Chiroptical Properties of Binaphthyl-Hinged [5]Helicenes

The synthesis, structure, and circularly polarized luminescence (CPL) of two types of shape-persistent [5]helicenes, hinged by a tethered (−OCH₂CH₂O−) or untethered (−OCH₃) binaphthyl, are reported. The binaphthyl tethering system facilitated an effective Wittig ring-closure reaction in the synthesis of a macrocyclic precursor, which could be easily converted to the title compound via successive photocyclization. The tethered groups were replaced with untethered −OCH₃ groups by treatment with BBr₃ followed by methylation. Both compounds exhibited similar spectra, and their longest wavelength absorption band with a low intensity was attributed to the transition from HOMO to LUMO+1. These compounds exhibited CPL with higher dissymmetry factors g_lum values than unlocked helicenes.     

Synthesis, structure and mesomorphic properties of side-chain chiral liquid crystalline polysiloxanes based on (S)-(+)-2-methyl-1-butanol derivatives

The synthesis of five chiral liquid crystalline monomers (M₁-M₅), and their corresponding side-chain polymers (P₁-P₅) based on (S)-(+)-2-methyl-1-butanol derivatives is described. The chemical structures of the monomers were confirmed by FT-IR, ¹H NMR, and elemental analyses. The structure-property relationships of the monomers and polymers obtained are discussed. The mesomorphic properties were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), polarizing optical microscopy (POM), and X-ray diffraction (XRD) measurements. All monomers showed a cholesteric phase. For M₂, M₃, and M₅, besides a cholesteric phase and a smectic A (S_A) phase, M₂ also revealed an enantiotropic chiral smectic C phase and a monotropic smectic B (S_B) phase, and M₃ also showed a S_B phase. The polymers P₁-P₅ exhibited a S_A phase, moreover, P₂, P₃ and P₅ also revealed a phase. The experimental results demonstrated that a flexible siloxane backbone and a long flexible spacer tended to exhibit a low glass transition temperature, high thermal stability, and wide mesophase temperature range.     

Visible Light and Temperature Regulated Reflection Colors in Self-supporting Cholesteric Liquid Crystal Physical Gels

Photo-responsive cholesteric liquid crystals (CLCs) have attracted much attention in recent years due to their wide applications in filters,tunable optical lasers,dynamic display devices,etc.However,UV light is usually used as the external stimulus source,which is not environment-friendly enough.On the other hand,the mechanical properties of CLCs are not strong enough for these practical applications.Therefore,it still remains a challenge to endow the CLCs with visible light response and high mechanical properties at the same time.Herein,an axially chiral tetra-fluorinated binaphthyl azobenzene gelator (S-4F-AG) is synthesized.Upon 550 and 450 nm light irradiations,S-4F-AG exhibits excellent photo-switchable behaviors.Notably,the maximum content of cis-isomer and its half-life are as high as 35％ and 89 h in acetonitrile,respectively.A self-supporting CLC physical gel with a storage modulus around 104 Pa can be obtained when 3wt％ S-4F-AG and 12wt％binaphthyl azobenzene derivative (dopant 2) are co-doped into a nematic LC host P0616A.This CLC physical gel exhibits a temperature-driven blue,green,and red reflection colors reversibly.Importantly,such three primary RGB colors can also be realized by adjusting the exposure time of 550 nm green light.This work lays a solid foundation for the applications ranging from information storage to high-tech anticounterfeit.     

pH值对邻苯二亚胺纤维素的制备及荧光性能的影响

制备了席夫碱（Ｓｃｈｉｆｆ’ｓ ｂａｓｅ）邻苯二亚胺纤维素（ＰＤＩＭＣ），考查ｐＨ值对制备反应和产物荧光性能的影响。结果表明：氧化度为１００％的二醛纤维素在ｐＨ＝７￣１３、室温下、反应３０ｈ生成的邻苯二亚胺纤维素，具有强较的荧光性能，熔点４１０ｋ，分解温度为５７８Ｋ；ＰＤＩＭＣ水溶液在ＰＨ＝７．６，浓度为７．６×１０＾－４ｇ／ｍＬ，２０℃时，Ｅｘ＝４７０ｎｍ，Ｅｍ＝５５５ｎｍ处荧光最强。     

电致蓝光芴取代聚芴的合成与光谱稳定性

为了筛选高效稳定的聚合物电致蓝光材料, 设计合成了三苯胺和芴取代的二芳基芴单体, 并通过Suzuki缩聚合成了交替共聚物TPAFF-co-F和TPAFF-co-P. 将二辛基芴引入聚芴的9位可以增加其溶解度, 同时具有屏蔽主链和减少主链芴9位被氧化的作用, 三苯胺基团将有利于提高空穴在阳极界面的注入能力. 200 ℃下空气中退火24 h实验表明, 在相同条件下, 绿光指数(Igreen/Iblue)顺序为聚(9,9-二辛基芴)(1.07)>TPAFF-co-F(0.65)>TPAFF-co-P (0.47), 证明了烷基芴引入减少了主链氧化的几率. 还制作了发光二极管器件, 其结构为ITO/PEDOT:PSS(40 nm)/TPAFF-co-F或TPAFF-co-P(80 nm)/Ba(4 nm)/Al(120 nm). 在高电流密度下它们保持了良好的光谱稳定性, 在547 mA·cm-2电流密度下, TPAFF-co-F的CIE(国际发光照明委员会)坐标为(0.22, 0.24), TPAFF-co-P的CIE坐标为(0.24, 0.26), 后者的电流效率为0.712 cd·A-1.