手性液晶材料的研究进展

介绍了手性液晶的发展过程,阐述了手性液晶的结构、分类与应用研究的现状,着重讨论了手性液晶在显示用液晶材料中的重要作用及应用,并对手性液晶的发展前景做了展望。     

Synthesis,structure, and phase behavior of new chiral liquid‐crystalline polysiloxanes based on mesogenic menthyl monomers

Six new chiral monomers ( M ₁ – M ₆ ), and their corresponding side chain polymers ( P ₁ – P ₆ ) containing menthyl groups were synthesized. The chemical structures of M ₁ – M ₆ were characterized with FTIR and ¹H NMR. The structure–property relationships of the monomers and polymers obtained are discussed. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X‐ray diffraction measurements. Some compounds containing menthyl groups formed mesophase when a flexible spacer was inserted between the mesogenic core and the menthyl groups by reducing the steric hindered effect. The monomers M ₁ , M ₄ , and M ₅ did not reveal mesomorphic properties because of the weaker rigid core or the longer flexible terminal groups, whereas M ₂ , M ₃ , and M ₆ all revealed cholesteric phase. Except P ₄ and P ₅ , the homopolymers P ₁ – P ₃ and P ₆ showed a smectic A phase. In addition, melting, glass transition temperature, or clearing temperature increased, and the mesophase temperature range widened with increasing the rigidity of mesogenic core or decreasing the length of the flexible spacer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and photopolymerization of acrylic acrylate copolymers

Acrylate‐functionalized copolymers were synthesized by the modification of poly(butyl acrylate‐co‐glycidyl methacrylate) (BA/GMA) and poly(butyl acrylate‐co‐methyl methacrylate‐co‐glycidyl methacrylate). ¹³C‐NMR analyses showed that no glycidyl methacrylate block longer than three monomer units was formed in the BA/GMA copolymer if the glycidyl methacrylate concentration was kept below 20 mol %. We chemically modified the copolymers by reacting the epoxy group with acrylic acid to yield polymers with various glass‐transition temperatures and functionalities. We studied the crosslinking reactions of these copolymers by differential scanning calorimetry to point out the effect of chain functionality on double‐bond reactivity. Films formed from acrylic acrylate copolymer precursors were finally cured under ultraviolet radiation. Network heterogeneities such as pendant chains and highly crosslinked microgel‐like regions greatly influenced the network structure and, therefore, its viscoelastic properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 753–763, 2002     

New side‐chain nematic liquid crystalline elastomers containing smectic crosslinking units

A series of siloxane‐based liquid crystalline elastomers containing the smectic crosslinking agent M‐1 and nematic monomer M‐2 were synthesized by a one‐step hydrosilication reaction. The chemical structures of the monomers and polymers obtained were confirmed by FTIR spectroscopy. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X‐ray diffraction (XRD) measurements. The influence of the crosslinking unit on the phase behavior was discussed. The experimental results demonstrated that the glass transition temperatures of elastomers had no remarkable change, and isotropization temperatures decrease with increasing the content of the crosslinking agent M‐1. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3755–3760, 2004     

Synthesis and characterization of a series of smectic liquid crystalline elastomers

A series of new smectic and cholesteric liquid crystalline elastomers was prepared by graft polymerization of mesogenic monomer with the chiral and nonmesogenic crosslinking agent using polymethylhydrosiloxane as backbone. The chemical structures of the monomers and polymers obtained were confirmed by Fourier transform infrared (FTIR), proton nuclear magnetic resonance spectra (¹H‐NMR). The mesomorphic properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X‐ray diffraction measurements (XRD). M₁ showed smectic (S_B, S_C, S_A) and nematic phases during the heating and the cooling cycles. Polymer P₀ and elastomer P₁ exhibited smectic B phase, elastomers P₂–P₅ showed smectic A phase, P₆ and P₇ showed cholesteric phase, and P₈ displayed stress‐induced birefringence. The elastomers containing less than 15 mol % M₂ displayed elasticity and reversible phase transition with wide mesophase temperature ranges. Experimental results demonstrated that the glass transition temperatures decreased first and then increased; melting temperatures and the isotropization temperatures and the mesophase temperature ranges decreased with increasing content of crosslinking unit. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 498–506, 2005     

Effect of the different rigidity of the chiral crosslinker on phase behaviors of side‐chain chiral liquid crystalline elastomers

In the present work, the phase behaviors of two series of side‐chain liquid crystalline elastomers ( PI and PII series) derived from the same nematic liquid crystalline monomer and the different rigidity of chiral bisolefinic crosslinking units have been compared and studied extensively, and the effect of the different rigidity of crosslinker on the phase behavior of elastomers has been discussed. The chemical structure of the monomers and polymers obtained were confirmed by FTIR and ¹H NMR spectroscopy. The phase behaviors were investigated by differential scanning calorimetry, polarizing optical microscopy measurement, thermogravimetric analyses, and X‐ray diffraction measurement. The two series of elastomers showed smectic or cholesteric phases. When the amount of different crosslinking units was less than 15 mol %, both of the elastomers displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. It is shown that the isotropization temperature values of PII series are higher than those of PI series, and the glass transition temperature values of PII series varied smoothly and that of PI series changed smoothly first and then abruptly with increasing the contents of crosslinkers with different rigidity. In addition, PI series showed an interesting change in LC texture near clearing point, but PII series did not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

一种手性薄荷单体对侧链液晶聚合物性能的影响研究

由非液晶手性薄荷单体M1和胆甾醇类液晶单体M2与聚甲基含氢硅氧烷（PMHS）接枝共聚合成了系列新型侧链液晶聚合物。运用红外光谱分析（FTIR）、氢核磁共振谱分析（1H NMR）、差示扫描量热分析（DSC）、热失重（TG）分析、偏光显微分析（POM）、旋光分析（SORT）和X-射线衍射分析（XRD）等进行表征。单体M2在升温和降温过程中呈现胆甾相液晶织构，M2均聚物P1为手性近晶A相，P2～P7为胆甾相液晶。实验结果显示，随着单体M1含量的增加，聚合物的左旋光活性越来越强，玻璃化温度强呈现先降低后升高趋势，清亮点温度Ti降低，液晶相范围变窄。     

In-situ photopolymerization of an oriented chiral liquid crystal acrylate in an electric field

Summary The effect of an external electric field on the photopolymerization rate of chiral liquid crystalline 4-acryloyloxy-undecanloxy-4'-[S(-)-2-methylbutyloxy]-biphenyl (monomer (I)) was studied using FT-IR. The orientation behavior of the thermally polymerized polyacrylate of monomer (I) under an electric field was observed by POM. The results showed that in-situ photopolymerization of the oriented monomer (I) under the application of an electric field proceeded at a higher rate than in the absence of an electric field and can fix mesogenic orientation.     

Comparative study on the electrooptical properties of polymer‐dispersed liquid crystal films with different mixtures of monomers and liquid crystals

This article deals with the study of polymer‐dispersed liquid crystal (PDLC) films that consisted of microdroplets of liquid crystals (LCs) dispersed in a polymer matrix. The PDLC films were fabricated by the photoinduced phase separation method under room‐temperature conditions. To determine the extent of the effects of the molecular structures and their physical properties of different mixtures of monomers and LCs on the morphology and electrooptical properties of the PDLC films, various mixtures were used. A detailed discussion of the obtained results is given. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚丙烯/热致性液晶聚合物原位复合材料的研究进展

聚丙烯是一个通用塑料,为了提高聚丙烯的性能,拓宽其应用领域,人们对聚丙烯进行了改性研究.笔者简述了热致液晶聚合物原位复合改性聚丙烯的研究进展,并讨论热致液晶聚合物对聚丙烯结晶与熔融行为、微观结构、流变性及力学性能的影响,介绍了改进TLCP与PP之间相容性的常用方法.最后对TLCP/PP原位复合材料的发展提出一些看法.     

Synthesis and phase behavior of new cholesteric liquid‐crystalline copolymers containing chiral mesogenic groups derived from menthol derivatives

The synthesis of a new chiral mesogenic monomer ( M₁ ), a nematic monomer ( M₂ ), and a series of side chain cholesteric copolymers ( P₂ – P₆ ) containing the mesogenic menthyl groups is described. The chemical structures of the compounds were confirmed by FTIR and ¹H NMR. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, thermogravimetric analysis, and polarizing optical microscopy. M ₁ showed an enantiotropic cholesteric phase, and M₂ revealed a nematic phase. The homopolymers P₁ and P₇ , respectively, displayed a chiral smectic A (S_A) phase and a nematic phase, while the copolymers P₂ – P₆ exhibited the Grandjean texture of the cholesteric phase. T_g, T_i, and ΔT of P₁ – P₇ increased with increasing the concentration of M₂ in the polymers. All of the obtained polymers displayed very good thermal stability and the wide mesophase temperature range. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nanostructures generated from photopolymerization of poly(ethylene glycol) diacrylate templated from hexagonal lyotropic liquid crystals

The use of lyotropic liquid crystals (LLC) as a template to form periodic nanostructures in polymer materials is a promising technology. In this study, cross‐linked poly(ethylene glycol) diacrylate nanostructured materials were prepared by photopolymerization in LLC hexagonal phases. Polarized light microscopy and small‐angle powder X‐ray diffraction were used to understand the original LLC order retention on photopolymerization, and scanning electron microscope was used to investigate the morphology under different purifying solvents and drying conditions. A Quantachrome Autosorb 1 system was used to study the pore size distribution of samples. It was found that the LLC hexagonal structure was retained to a great extent after photopolymerization. The formation of nanostructures was affected by purifying solvent and drying condition. The nanostructure synthesized from LLC with favorably aligned nanopores will find increasing applications in gas and water filtration, biology, and health science. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polymer molecular weight and chain transfer during the photopolymerization of an aliphatic monoacrylate in a smectic liquid crystal

Polymer/liquid crystal (LC) composites offer a unique opportunity to study polymerizations in ordered media, specifically the potential effect mesophase order can have on polymer properties including molecular weight. To develop successful polymer/LC composites for display applications, it is important to understand the effect of mesophase order on polymer molecular weight in order to optimize the electro-optic (EO) properties of the polymer/LC composite. Polymer molecular weight may be influenced in a LC by changes in polymerization rate as LC order is modulated and by chain transfer. This work focuses on the photopolymerization of an aliphatic monoacrylate monomer, decyl acrylate (DA), both in the ordered LC phases of 8CB as well as in isotropic solutions with LC and co-solvent.When DA is polymerized using the LC as the solvent, enhanced polymerization rates and polymer molecular weights are observed in the highly ordered smectic phase compared to the less ordered nematic and isotropic phases. When conducted strictly in an isotropic environment using a co-solvent with increasing 8CB percentages, a dramatic decrease in the polymerization rate and a significant reduction of the polymer molecular weight is observed, implying degradative chain transfer to the LC. NMR results show that this chain transfer is a result of hydrogen abstraction from the liquid crystals, which leads to the reduction in the polymerization rate with increasing 8CB concentration. The most likely site of hydrogen abstraction is from the benzyl hydrogens of the alkyl chain of 8CB. This chain transfer also plays a role for polymerizations performed in the ordered phases of the LC. Chain transfer appears to be less significant when polymerizations are conducted in the smectic phase due to the anti-parallel association of the LC molecules. When polymerizations occur in the less ordered phases, chain transfer dominates leading to a large reduction in polymer molecular weight and polymerization rate.     

Initiator‐free photopolymerization of common acrylate monomers with 254 nm light

Using an available light source at a wavelength of 254 nm, common acrylate monomers were polymerized without any photoinitiators, which was confirmed using Fourier transform IR (FTIR) spectroscopy, ¹H NMR, gel permeation chromatography and fast atom bombardment mass spectrometric measurements. It was found that phenyl acrylate shows higher conversion than n‐ and t‐butyl acrylates. A trifunctional acrylate was also used for UV curing. The cured films were fabricated successfully on different kinds of substrates by using a batch‐ or conveyor‐type irradiation apparatus. It is indicated from FTIR spectral measurements that ca 40%–50% of acryloyl groups are consumed by the photopolymerization. Oxygen concentration in the sample chamber influences the photopolymerization, indicating that the polymerization proceeds via a radical process. © 2018 Society of Chemical Industry     

The kinetics of vinyl acrylate photopolymerization

The photopolymerization of vinyl acrylate has been investigated using real-time FTIR. The acrylate and vinyl groups exhibit different polymerization kinetics with the acrylate functionality polymerizing at a much faster rate. Vinyl acrylate not only self-initiates its own free-radical polymerization, but also photoinitiates the polymerization of mono- and difunctional acrylates. Kinetic studies using a model monomer system indicate that it is essential for the acrylate and vinyl group to be part of the same molecule in order to function as an effective initiator for acrylate polymerization.     

Synthesis,Characterization and Texture Observations of Calamitic Liquid Crystalline Compounds

Several divinylic mesogenic monomers were synthesized based on coupling the monomer 4-(4-pentenyloxy)benzoic acid with chlorohydroquinone, 2,5-dihydroxy- acetophenone, methylhydroquinone or 2-methoxyhydroquinone. This resulted in novel mesogens of phenylene esters with different lateral substituent groups. The effect of the lateral substituent group on the thermotropic phase behavior for these liquid crystalline compounds was investigated using DSC and optical polarized microscopy. All the mesogens proved to have a wide nematic liquid crystalline range. Only the phenylene ester, which has a methoxy lateral substituent, exhibited both nematic and smectic phases. Structural confirmation of all new derivatives was accomplished by ¹H- and ¹³C-NMR spectroscopic analysis, along with CH elemental analysis.     

A novel porous epoxy acrylate resin monolith prepared by the low-temperature phase separation photopolymerization

A novel porous epoxy acrylate resin monolith has been successfully prepared by low-temperature phase separation photoinitiated polymerization. The process parameters of low-temperature photopolymerization, including photoinitiators type, concentration, and sample thickness were studied. The optimum conditions for the preparation of the sample were also evaluated. The results showed that the porous morphology of the prepared monolith was affected by monomer concentration, freezing speed and temperature of the solution. The average pore size increased with increasing solvent amount, decreasing freezing temperature and speed.     

Main‐chain chiral smectic liquid‐crystalline ionomers containing sulfonic acid groups

Three series of main‐chain liquid‐crystalline polymers (P1, P2, and P3) were synthesized by an interfacial condensation reaction of sebacoyl dichloride with various amount of brilliant yellow, isosorbide, and 4,4′‐biphenydiol. P1 series are polyesters prepared from sebacoyl chloride and various amount of 4,4′‐biphenyldiol and isosorbide. P2 series are polyesters prepared from sebacoyl chloride and various amount of 4,4′‐biphenyldiol, brilliant yellow, and isosorbide. P3 series are polyesters prepared from sebacoyl chloride and various amount of 4,4′‐biphenyldiol and brilliant yellow. P2 and P3 are main‐chain liquid‐crystalline ionomers. P1₂ and P3 series were prepared as model polymers for comparison with the liquid crystalline behavior of ionomers, P2 series. The structures of the polymers were characterized by IR and UV spectroscopy. Differential scanning calorimetry was used to measure the thermal properties of the polymers. The mesogenic properties were investigated by polarized optical microscope, differential scanning calorimetry, and X‐ray diffraction measurements. The results show that P2 series are chiral smectic C (S_mC*) and chiral smectic B (S_mB*) liquid crystalline ionomers exhibiting broken focal‐conic texture and schlieren, as is the polymer P1₂, which has the same amount of 4,4′‐biphenydiol and isosorbide. The introduction of ionic units in P2 series leads to an increase of clearing point, but has not affected the mesogenic type and texture, as compared with the corresponding polymer P1₂. The introduction of chiral units in P2 series leads to a change of mesophase, as compared with P3 series, which exhibit smectic C mesogetic phase. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1254–1263, 2006     

Synthesis of novel macrophotoinitiator for the photopolymerization of acrylate

A new kind of macrophotoinitiator (MPI) was synthesized through the copolymerization of acrylic monomers and the polymerizable photoinitiator monomer 2959‐AA. Monomer 2959‐AA was obtained by an esterification reaction between acrylic acid (AA) and the water‐soluble photoinitiator Irgacure 2959 [2‐hydroxy‐4‐(2‐hydroxyethoxy)‐2‐methylpropiophenone]. By adjusting the monomer proportions in the MPIs, two series of MPIs with different 2959‐AA contents and different glass transition temperatures were obtained. The molecular structure of 2959‐AA was characterized by Fourier‐transform infrared spectroscopy, nuclear magnetic spectrometry, and mass spectrometry. Polymerization of 1, 6‐hexanediol diacrylate was initiated using Irgacure 2959 and 2959‐AA, and two series of MPIs to be polymerized were studied with a photo‐DSC test. Results showed that 2959‐AA had higher chemical reactivity than Irgacure 2959 because of the higher solubility of the former. It was evident from the experiments that 2959‐AA content in the MPI progressively increased the polymerization rate and monomer conversion when the glass transition temperatures of MPIs were similar. At the same 2959‐AA content, the polymerization rate slightly slowed down with increased glass transition temperature. However, the radical lifetime and polymerization time were prolonged. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40352.     

纤维素及其衍生物作为高效液相色谱手性固定相的研究进展

对纤维及其衍生物作为高效液相色谱手性固定相的研究进展进行了综合综述。