含对硝基偶氮苯基团的侧链液晶高分子的合成及其光致变色性能研究

报道了新型的含对硝基偶氮苯基团的甲基丙烯酸酯单体与含介晶基团的甲基丙烯酸酯单体的合成及其自由基共聚合．利用１Ｈ ＮＭＲ、ＩＲ、ＵＶ Ｖｉｓ、ＧＰＣ、元素分析、ＤＴＡ及ＰＯＭ等手段对偶氮单体和聚合物进行了结构表征．证明两种单体的共聚合产物为无规共聚物，而且各聚合物在加热过程中均显示出明显的向列相液晶织构．研究了偶氮单体及其与介晶单体的共聚物的氯仿溶液和聚合物薄膜在紫外光诱导下的光异构化及热回复异构化行为．结果表明，它们在紫外光诱导下均能发生光致变色现象，而且介质对其光化学行为起决定作用．     

SYNTHESIS AND CHARACTERIZATI0N OF POLYMETHACRYLATES BEARING HETEROCYCLIC AZO GROUP AND MESOGENIC GROUP FOR NONLINEAR OPTICS

The methacrylate monomers bearing mesogenic group and heterocyclicazo dye have been synthesized. The monomeric dye was copolymerized with the mesogenicmonomer using a free radical initiator to produce polymers useful for nonlinear optics. Themonomers and polymers were characterized by IR, ~1H-NMR, and UV-Vis spectra. Theaverage molecular weight (M_w and M_n) of the polymers were determined by gel permeationchromatography. The thermal properties of the polymers such as thermal stability andphase transition behavior were studied by thermogravimetric analysis, differential thermalanalysis, polarizing optical microscope and X-ray diffractometer. The results demonstratethat the synthesized polymers are crystalline polymers at room temperature and no liquidcrystalline phases were observed for all of them.     

含对甲氧基苯氧羰基偶氮苯基团的侧链液晶高分子的合成与表征

报道了新型的含对甲氧基苯氧羰基偶氮苯基团的甲基丙烯酸酯单体与含对甲氧基苯氧羰基苯基团的甲基丙烯酸酯单体的合成及其自由基共聚合．利用１Ｈ ＮＭＲ、ＩＲ、ＵＶ Ｖｉｓ、元素分析、ＧＰＣ、ＴＧ ＤＴＡ、ＰＯＭ及Ｘ 射线衍射等手段对偶氮单体及聚合物的结构与性能进行了表征,证明两种单体的共聚合产物为无规共聚物,而且各聚合物均具有较好的热稳定性．研究结果还表明,偶氮单体与聚合物在升温过程中均显示出向列相液晶织构,且聚合物的液晶相范围随偶氮含量的增加而变宽．     

手性聚甲基丙烯酸酯液晶聚合物的合成及相行为的研究

手性聚甲基丙烯酸酯液晶聚合物的合成及相行为的研究向前，张纪宇，张树范（中国科学院化学研究所北京１０００８０）关键词手性液晶聚合物，相行为手性侧链液晶聚合物在侧链中含有不对称碳原子的末端基，使聚合物显示Ｓｔ相．Ｓ？相层中的分子呈倾斜排列而产生自发极化．...     

偶氮苯为探针的液晶聚合物聚集形态研究

利用紫外-可见光谱,对比研究了尾挂侧链液晶聚合物和腰挂侧链液晶聚合物在结晶相和液晶相转变过程中的液晶基元取向情况.研究表明,石英基材表面倾向于诱导偶氮液晶基元垂直于基材排列;观察到了在液晶态尾挂侧链液晶聚合物和腰挂侧链液晶聚合物的不同取向行为.在室温下重新结晶数天后,腰挂液晶聚合物的紫外可见光谱缓慢回复.     

Unusual electro-optical behaviour of the nematic polyacrylate

ABSTRACT

High sensitivity of liquid crystals to the electric field makes them highly demanded and widely used in different applications. Despite the large number of the electro-optical research on the low-molar-mass liquid crystals electro-optics of the liquid crystalline (LC) polymers is much less studied. Herein, the comparative electro-optical behaviour of two nematic comb-shaped polyacrylates with phenylbenzoate mesogenic side groups was studied in detail. These two polyacrylates have completely the same structure of polymer backbone and spacer length but different in the direction of the ester group in the phenylbenzoate fragments. It was found that this difference predetermines their completely opposite electro-optical properties.

The influence of the electric field of different strength and frequency on the orientation of the mesogenic groups of these polymers is studied. It is shown that application of the electric field at temperatures above the glass transition temperature (~25°C) induces reorientation of the mesogenic groups along or perpendicular to the electric field direction depending in its turn on the ester group direction. For one of the polyacrylates an unusual textural transition is found; during cooling of the polymer sample under applied field at definite temperature a sharp change in the mesogen’s orientation from homeotropic to planar one is found. This electro-optical phenomenon is observed for the first time and probably associated with sharp change in sign of anisotropy of dielectric permittivity from positive (at high temperatures) to negative one (at lower temperatures). Kinetics of the electro-optical switching at different temperatures, influence of the molar masses of the polymer and frequency of the applied AC field on electro-optical behaviour of the polymers are studied. The possibility of the fixation of the electroinduced homeotropic alignment of the mesogenic groups by photopolymerisation of the diacrylate dissolved in the polymer is demonstrated.     

THE EFFECT OF SUBSTITUENT ON THE THERMAL PROPERTIES OF POLYESTERS CONSISTING OF AROMATIC TYPE SCHIFF BASE MESOGENIC UNITS AND POLYMETHYLENE SPACERS

Polyesters consisting of substituted aromatic type Schiff base mesogenic unit andpolymethylene spacers were synthesized and their thermal transitions and liquid crystallineproperties were studied. The liquid crystalline behaviour has been characterized by differentialscanning calorimetry (DSC) and optical polarizing microscopy. Structural broadening bysubstitution of methoxy group in 2, 2" positions of the mesogenic core produce polymers withlower transition temperatures. Polymers synthesized from ortho and meta substituted phenylenediamine did not form a liquid crystal phase.     

Synthesis and characterization of chiral azo LCPs with optical properties

ABSTRACT

In this study, we designed, synthesised and characterised two series of cholesteric liquid crystal polymers, QP series and ZP series. With polymethylhydrosiloxane as the main chain, QP series were synthesised by copolymerisation between the monomer M₁ containing a cholesteryl mesogenic unit and the monomer M₂ with a hydroxyl. ZP series, meanwhile, were synthesised by esterification between QP series members and the monomer M₃, a carboxylic acid with an azo mesogenic unit. We characterised chemical structures of all the monomers and polymers by FT-IR and ¹H-NMR, which proved that the target monomers and polymers had been obtained. We observed dramatic colour changes after the introduction of monomer M₃ and Grandjean textures from both QP series and ZP series using POM. In addition, strong selective reflection could be observed as well. Then, we characterised the thermal properties of polymers by DSC, TGA and XRD to explore their phase transition behaviours further. Their photoresponsive and photochromic properties were characterised by UV-Vis spectrum.     

含对甲氧基苯氧羰基偶氮苯基团的侧链液晶高分子的光致变色性能研究

研究了含对甲氧基苯氧羰基偶氮苯基团的甲基丙烯酸酯单体及其与含对甲氧基苯氧羰基苯基团的甲基丙烯酸酯单体的共聚物的氯仿溶液、二甲基甲酰胺溶液和共聚物薄膜在紫外光诱导下的光异构化及热回复异构化行为。结果表明,它们在紫外光诱导下均能发生先致变色现象,且介质对其光致变色行为起决定作用。     

Liquid-crystalline side chain polymethacrylates II. Variation of spacer and central linkage in nitro-terminated polymers

The thermal behaviour and the mesogenic properties of liquid-crystalline side chain polymers with the structure are described with n = 3, 6, 8 or 11 and Z = -COO-, -CONH- or -N=N-. The polymers were made by radical chain polymerization. Most of them exhibit smectic phases, nematic phases were not observed. The amide linkage which has not yet been described as a structural element in such polymers gives rise to polymers of high polarity and high glass transition temperatures (T_g). In all cases the amide polymers produced the highest T_g values, the ester polymers showing the lowest. The azo polymers exhibited the largest mesophase ranges and the highest clearing temperatures (T_c1) of all the materials investigated. Whereas the T_c1 values for the azopolymers are nearly independent of the length of the spacer those of the amide and ester polymers show rising clearing points with increasing spacer length.     

胆甾侧链聚硅氧烷高分子液晶的合成与相行为研究

本工作利用双键与Si-H键的加成反应合成了以丙烯酸胆甾醇酯为侧链的硅氧烷梳状聚合物液晶ECS.聚合物的结构得到了核磁与红外分析的证明.偏光显微镜和DSC对ECS的相态转变研究表明,ECS在一定的温度范围内能够形成液晶相,液晶相的存在范围与聚合物的结构密切相关.     

Side-chain liquid crystalline polyesters derived from diethylmalonate and/or 1,3-propanediol

A series of azo monomers for polycondensation have been synthesized and characterized. These monomers, which contain electron-donor or acceptor substituents, have been condensed with aliphatic monomers to obtain two different series of aliphatic main-chain polyesters with pendant mesogenic groups. The polymers display nematic or smectic phases depending on the structural modifications of pendant mesogenic groups and the length of the flexible main-chain. In addition to these series, two polyesters with a high concentration of side pro-mesogenic groups have been synthesized. © 1996 John Wiley & Sons, Inc.     

The effect of chemical constitution of mesogenic monomer unit on liquid crystalline properties of polymers

Glass transition temperatures and thermodynamic parameters of mesophase melting of polymers with mesogenic side-groups of the phenyl benzoate class depend on the length of the alkoxy substitutent, the mobility of the mesogenic groups and the nature of the main chain. Polymers with mesogenic groups connected directly to the main chain, obtained by precipitation from solution, have equilibrium liquid crystalline structures in which the macromolecules exist in a compact coil conformation with an ordered arrangement of the mesogenic groups. The nature of the main chain of these polymers affects the liquid crystalline structure. Mesophase melting parameters of the polymers with mesogenic groups, connected by flexible spacer groups to the main chain, are almost independent of the thermal history of the samples. These polymers in the isotropic melts are assumed to contain aggregates of the mesogenic groups.     

Silicon‐containing azo polymers with paired mesogens and their applications to optical memory media

We synthesized a novel photoresponsive monomer, silicon‐containing azo monomer with paired mesogens in the side chain, by reacting 3‐methacryloxypropylmethyldichlorosilane with 2‐[2‐(4‐cyano‐azobenzene‐4′‐oxy)ethylene‐oxy]ethyl alcohol, a mesogenic group. Corresponding homopolymer and copolymers with methyl methacrylate were generated via radical polymerization with AIBN as a radical initiator. Investigations of their thermal properties and optical textures confirmed the monomer and the homopolymer have smectic structures. Homo‐ and copolymer films showed high potential as reversible data recording media via photoinduced alignment of azobenzene groups with irradiation of a linearly or circularly polarized light. Out of all the samples, the copolymer films with high azo dye contents showed the best resolution in the recorded data as well as the fastest response to a pump beam due to large optical birefringence induced in a write‐in process. Strong dependence of the stability of the data stored in the films on the glass transition temperature of the polymers was also observed. In addition, high‐quality holographic grating patterns were inscribed even on the copolymer film with azo molar content of only 7.0% using a modified two‐wave mixing technique. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6734–6745, 2008     

Liquid crystalline side chain polymer with a poly (Geraniol-co-MMA) backbone and phenylbenzoate mesogenic group: synthesis and characterization

A new side chain liquid crystalline polymers have been synthesized and characterized in which [geraniol-co-MMA] polymer are used as a backbone linked via polymethylene spacer to phenyl benzoate mesogenic group. The polymer exhibits enantiotropic liquid crystallinity with nematic phase and does not exhibit side chain crystallization .A clear difference between the nature of the mesophase is evidenced between [Geraniol-co-MMA] main chain and methacrylate polymers .The LC polymer exhibit glass transition at 40 °C. In a comparative analysis, we discuss the relevance of polymer backbone in the synthesis of side chain liquid crystalline polymers.     

Adhesive liquid-crystalline polymers

The synthesis and characterization of liquid-crystalline polymers with possible good adhesive properties is reported. These polymers are prepared by alternating copolymerization of maleic anhydride and mesogenic alkenes. The spacer length m is varied (m = 2, 3, 4, 6, 8 and 9) and methoxybiphenyl is used as the mesogenic group. The glass transition temperature decreases and the isotropization temperature increases with spacer length. Depending on the spacer length and temperature, S_B and S_Ad mesophases can be observed. After annealing, spin-coated films of these polymers show very regular layered structures with a layer spacing similar to that in the bulk.     

聚苯乙烯基偶氮聚合物的合成研究

改进了聚苯乙烯的硝化、还原、重氮化和偶合反应路线 (NRDC) ,使每步反应都得到很高的产率 ,并利用大分子重氮盐 (MDS)分别与苯胺、N 烃基苯胺和酚等三类化合物偶合 ,得到相应的聚苯乙烯基偶氮聚合物 .核磁共振分析结果证明了产物的高偶联率 .通过对大分子重氮盐热稳定性的研究 ,发现偶合反应之后需要一步加热反应以消除残余重氮基团 .还研究了这些聚合物的紫外 可见吸收光谱性质 ,氨 (胺 )基偶氮产物的水溶液表现出了明显的pH敏感性     

Influence of different linkage groups in biphenyl mesogenic core on phase behaviors of mesogen‐jacketed liquid crystalline polymers

The work focuses on the design, synthesis, and characterization of a series of mesogen‐jacketed liquid crystalline polymers (MJLCPs) based on the octyl substituted biphenyl mesogenic core through different linkage groups. The molecular characterizations of the polymers obtained by conventional free radical polymerization were performed with ¹H NMR, gel permeation chromatography, and thermogravimetric analysis. Their thermotropic liquid crystalline (LC) behaviors were investigated in detail by a combination of various techniques, such as polarized light microscopy, differential scanning calorimetry, and 1D and 2D wide‐angle X‐ray diffraction. Our results showed that all the polymers were thermally stable, and their LC phases were greatly dependent on the linking groups between the biphenyl mesogenic core and terminal alkyl group substituent. Polymers with ether/ester or ether linkage group exhibited an unusual phase behavior with temperature increasing, tetragonal columnar nematic LC phase, or columnar nematic phase developed at high temperatures for the polymers transformed into amorphous phase during cooling process, showing a re‐entrant phase behaviors. However, polymers with ester linkage group were not LC with temperature varied. It is illustrated that subtle changes in the molecular structure brought about tremendous variation of the LC phase properties for MJLCPs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2545–2554     

Theory of main chain nematic polymers with spacers of varying degree of flexibility

Main chain liquid crystal polymers are modelled as either worms or jointed rods. In reality they are composed of mesogenic units (rods) linked by spacers with varying degrees of flexibility. We present a molecular model to describe non-homogeneous nematic polymers. The model takes account of molecular parameters, such as the lengths of the mesogenic group and the spacer units, and the interactions between them. The spacers are found to have an order differing from the mesogenic units. If the spacer is not very long and thus in effect is inflexible, one end of the spacer can retain to some extent the orientation of the other end, allowing orientational correlation between spacers mediated by the intermediate mesogenic unit. This is important in giving the chain a global rod-like behaviour as the nematic field becomes strong or the temperature low. The nematic order of the two components (mesogens and spacers), the nematic-isotropic transition as well as the latent entropy are examined. Furthermore, the anisotropic conformations of the polymers are investigated, which show either rod-like or random walk behaviour. Comparison of our results with experiment is found to be satisfactory.     

用含偶氮基的聚苯乙烯大分子引发剂合成两亲性嵌段共聚物

采用含偶氮基的聚苯乙烯预聚物（ＰＳ ＡＣＰＣ）作为引发剂，合成了苯乙烯（Ｓｔ）分别与甲基丙烯酸（ＭＡＡ）、甲基丙烯酸（β 羟丙酯）（ＨＰＭＡ）的嵌段共聚物，考察了ＰＳ ＡＣＰＣ引发第二单体的聚合反应行为，以及影响第二单体转化率和均聚物含量、共聚物组成的因素．用溶解性、凝胶渗透色谱（ＧＰＣ）、红外光谱（ＩＲ）、核磁共振（ＮＭＲ）、动态接触角（ＤＣＡ）等表征了嵌段共聚物．