Hydroxy-functionalized liquid-crystalline polyazomethines I. Synthesis, characterization and structure-mesogenic behaviour relationship

A new series of polyazomethines based on hydroxy-functionalized mesogenic units has been synthesized and characterized. Different structural variations have been checked in order to obtain mesogenic polyazomethines with low melting temperatures and a broad nematic range. Completely conjugated mesogenic units with a lateral substituent or alteration of coaxiality are shown to be the most suitable structural variations. No mesogenic behaviour was observed for polyazomethines with a flexible mesogenic core due to unfavourable conformational equilibrium. Polyazomethines have complex thermal behaviour and show an increase in the degree of polymerization on annealing.     

Multiple length scale self-organization in liquid crystalline block copolymers

A series of block copolymers were prepared consisting of a block of poly(styrene) and a block in which a mesogenic group was attached by polymer analogous chemistry to a flexible backbone. Two types of mesogenic groups which produced a range of mesophases were investigated: (i) an azobenzene mesogenic group and (ii) a semifluorinated group. Organization caused by liquid crystallinity and phase separation leads to simultaneous organization on a variety of length scales. Comparison of the ordering behavior of these two types of mesogenic groups and more conventional flexible chain diblocks are made.     

含两种不同介晶基团的半刚性共聚酯液晶态的结构研究

用Ｘ－光衍射，偏光显微镜及ＤＳＣ对含两种不同长度介晶基团４，４’－联苯二酚（Ⅰ）和对苯二甲酸二（对羟苯基）酯（Ⅱ）的系列共聚酯的液晶态进行了表征，据其液晶态中两种介晶单元的堆砌方式提出了可能的模型，这种模型很好地解释了液晶态的Ｘ－光衍射分布．     

Effect of shape of mesogenic group on the formation of liquid crystalline phase in polymers

Mesomorphic behaviour of four polymethacrylates with mesogenic side groups has been studied. In contrast to monomers which are nematogenic, mesogenic groups in the polymers form layer structures of the smectic type. A thermodynamic stable mesophase is supposed to be realized in polymers which consist of macromolecules of secondary structure, considering a macromolecule as the smallest structural element of the polymer system.     

Side chain polysiloxanes with fluorinated mesogenic groups. The role of the fluorine content on the properties of the smectic A state

A series of liquid crystalline polymers has been synthesized in which fluorinated or semi-fluorinated mesogenic moieties are used as side groups linked to a polysiloxane backbone. Clear-cut differences in the structure of the smectic A phase are evidenced between fluorinated polymers and their classical non-fluorinated homologues. In a comparative analysis, we discuss the relevance of the steric hindrance of perfluorinated sequences and of the microsegregation of the backbone in response to these modifications as related to the fluorine content in the side group and to the proportion of mesogenic groups.     

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.     

Preliminary communication Thermotropic liquid crystals of polyesters having a mesogenic p,p' -bibenzoate unit X. Distinct orientation of molecules in a thin SmCA film stretched from isotropic melt, providing evidence for the biaxiallity of the SmCA p

A thin oriented SmC film of a main-chain polyester was prepared by drawing from the A isotropic melt, and X-ray patterns were observed by irradiation from three characteristic positions relative to the film. The results clarify the biaxiallity of the SmC phase, with a A distinct molecular orientation where the mesogenic groups are tilted in a zigzag manner in a direction perpendicular to the film surface. Such a biaxial orientation is considered to result from the relaxation from the extended arrangement of the mesogenic groups on stretching to the stable zigzag arrangement.     

具有氟烷基边链和手性中心液晶化合物的合成及液晶性研究

本文设计合成了十个含氟烷基边链和手性中心的液晶化合物，并通过DSC和偏光显微镜对它们的液晶性进行了研究。其中二环系液晶化合物不显示液晶相或仅显示单边近晶A相。三环系液晶化合物中较长的氟烷基边链有利于近晶相的形成，且当液晶核另一端的烷氧基链的长度适中时，在氟烷基边链和液晶核之间具有手性中心的液晶分子显示了手性近晶C相和其它液晶相。     

含聚乙二醇柔性间隔段的主链型液晶聚酯的合成

分子结构与液晶行为间的关系是液晶性高分子物理问题研究的核心,通常的液晶性高分子中除液晶性基元外还引入一些相对来说很柔顺的链段,称作柔性间隔段．这是因为人们认识到高分子的液晶行为不只决定于液晶性基元的结构,也受到这些基元间以及基元和间隔段间相互作用的影...     

Supramolecular liquid crystals containing isoquinoline hydrogen-bonded acceptors

6-Dodecyloxyisoquinoline IS ( 1 ) has been synthesized and utilized as a proton acceptor to generate a series of novel mesogenic supramolecules. Two mesogenic supramolecular dimers IS-OBA and IS-COOBA have been constructed from a 1:1 molar ratio of IS complexed either with 4-decyloxybenzoic acid OBA ( 2 ) or with 4-decyloxycarbonylbenzoic acid COOBA ( 3 ). A kinked mesogenic supramolecular trimer, i.e. a double H-bonded complex (IS)-THDA, has been constructed from a 2:1 molar ratio of IS complexed with 2,5-thiophenedicarboxylic acid THDA ( 4 ). The mesogenic properties of the H-bonded complex (IS2)-THDA are compared with those of previously reported H-bonded complexes (C12PS)-THDA and (C12PP2)-THDA consisting of a 2:1 molar ratio of trans -4-dodecyloxy-4-stilbazole C12PS 2 ( 5 ) or 4-dodecyloxypyridine C12PP2 (6 ) with THDA. Significantly, the first isoquinoline-based supramolecular liquid crystals have been built, and their mesogenic properties have been introduced or modified by fused- N -heterocyclic rings.     

Towards Nematic Phases in Ionic Liquid Crystals – A Simulation Study

Ionic liquid crystals (ILCs) are soft matter materials with broad liquid crystalline phases and intrinsic electric conductivity. They typically consist of a rod-shaped mesogenic ion and a smaller spherical counter-ion. Their mesomorphic properties can be easily tuned by exchanging the counter ion. ILCs show a strong tendency to form smectic A phases due to the segregation of ionic and the non-ionic molecular segments. Nematic phases are therefore extremely rare in ILCs and the question of why nematic phases are so exceptional in existing ILCs, and how nematic ILCs might be obtained in the future is of vital interest for both the fundamental understanding and the potential applications of ILCs. Here, we present the result of a simulation study, which highlights the crucial role of the location of the ionic charge on the rod-like mesogenic ions in the phase behaviour of ILCs. We find that shifting the charge from the ends towards the centre of the mesogenic ion destabilizes the liquid crystalline state and induces a change from smectic A to nematic phases.     

Syntheses and properties of liquid crystalline N-substituted pyrroles and their polymers

Three liquid crystalline N-substituted pyrroles were synthesized from 6-(1-pyrrolyl)hexanol with phenolic derivatives having a mesogenic core of cyclohexylbenzene or biphenyl by Mitsunobu reaction. These pyrroles had two anodic peaks at 1.4 and 1.8 V (vs. SCE). The former was due to an oxidation of the pyrrole moiety and the latter was due to an oxidation of the mesogenic moiety. These pyrrole monomers were polymerized by electrochemical and chemical methods. The potentiostatic method and the chemical method using FeCl₃ gave a soluble and fusible polymer, respectively. A polymer having a mesogenic core of cyclohexyl benzene obtained by the chemical method and a polymer having a mesogenic core of biphenylketone obtained by the potentiostatic method had a liquid-crystalline phase. The phase was identified as smectic A by polarizing microscopy and XRD analysis. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2691–2698, 1998     

Liquid-crystalline polymer brushes: deformation and microphase segregation

A statistical theory of the structure and thermodynamics of a planar brush (‘accordion’) formed by bridged polymer chains containing mesogenic segments and immersed in a solvent is developed. It is shown that deformation of an accordion can lead to the formation of a two-phase structure with coexisting liquid-crystalline (LC) and swollen microphases. Phase diagrams for accordions with different grafting densities are obtained. The influence of anisotropic interaction between mesogenic segments on the structure of phase diagrams is investigated.     

Searching for photochromic liquid crystals Spironaphthoxazine substituted with a mesogenic group

A number of photochromic spiropyrans and spirooxazines containing mesogenic groups were synthesized. Only one of them, spiro-indoline-naphthoxazine with mesogenic substituent, 4-(4-heptylbenzoyloxy)benzoyloxy in 5-position, revealed mesomorphic properties. Its phase behaviour, photochromism and alignment in the electric field was investigated. A structure of the mesophase is discussed.     

Liquid-crystalline bisadducts of [60]fullerene

A second-generation cyanobiphenyl-based dendrimer was used as a liquid-crystalline promoter to synthesize mesomorphic bisadducts of [60]fullerene. Liquid-crystalline trans-2, trans-3, and equatorial bisadducts were obtained by condensation of the liquid-crystalline promoter, which carries a carboxylic acid function, with the corresponding bisaminofullerene derivatives. A monoadduct of fullerene was also prepared for comparative purposes. All the compounds gave rise to smectic A phases. An additional mesophase, which could not be identified, was observed for the trans-2 derivative. The supramolecular organization of the monoadduct derivative is governed by steric constraints. Indeed, for efficient space filling, adequacy between the cross-sectional areas of fullerene (approximately 100 A(2)) and of the mesogenic groups (approximately 22-25 A(2) per mesogenic group) is required. As a consequence, the monoadduct forms a bilayered smectic A phase. The supramolecular organization of the bisadducts is essentially governed by the nature and structure of the mesogenic groups and dendritic core. Therefore, the bisadducts form monolayered smectic A phases. The title compounds are promising supramolecular materials as they combine the self-organizing behavior of liquid crystals with the properties of fullerene.     

Alternative synthetic strategies for Schiff base derived liquid crystal polymers: A comparative study

Semiflexible liquid crystalline polymers based on Schiff bases as mesogenic cores have been synthesized through different synthetic strategies. The mesogenic cores are derived from 1,5-naphthalenediamine linked to a polymethylenic spacer by means of ether or ester groups. The synthetic strategies differ in the disconnection of the molecules to design the synthesis of the repeating units. Polymers were synthesized either as polyazomethines, where imine bonds are formed in the polymer synthesis, or as polyethers or polyesters, where the ether or ester groups are formed at the polymer-forming stage. The influence of the synthetic method and the linking groups between mesogenic core and flexible spacer on the thermal and mesogenic properties has been analyzed by DSC, thermogravimetry, and optical microscopy. The possibility of obtaining hydroxy-functionalized polymers by different synthetic strategies has been studied as well as the influence of these groups on the thermal and mesogenic properties. © 1996 John Wiley & Sons, Inc.     

Chiral liquid-crystalline copolyacrylates with biphenyl and phenyl benzoate side groups

The phase behavior and structure of liquid-crystalline phases of three series of copolymers with mesogenic units belonging to the families of biphenyls and phenyl benzoates have been studied, with the former mesogenic units containing a chiral center in a flexible spacer. A variation in the isotropization temperature as a function of composition is well described by the additivity rule, whereas the tilt angle of mesogenic groups in smectic layers changes nonlinearly. This angle decreases beginning from homopolymers and attains the minimum value for the copolymers of the equimolar composition, which show the highest ferroelectric activity among the polymer systems under study.     

Thermal properties and fracture toughness of a liquid‐crystalline epoxy resin cured with an aromatic diamine crosslinker having a mesogenic group

A mesogenic‐type curing agent was synthesized to introduce a mesogenic group not only into epoxy resin backbones but also into the crosslink units. In the mesogenic curing agent system, the domain size became larger, and the network arrangement in each domain existed to a greater extent than that in a system cured with the ordinary diamine curing system according to the evidence from polarized optical micrographs and polarized Fourier transform infrared mapping measurements. Moreover, the fracture toughness of the system was considerably improved. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2486–2494, 2006     

Synthesis and mesomorphic properties of cyanurates and isocyanurates. Branched mesogens as model crosslinks for liquid crystalline thermosets

A number of new s-triazines (cyanurates and isocyanurates) with diaromatic mesogenic branches have been synthesized and their thermal properties investigated. No liquid crystal phases were found in the series of isocyanurates, while the cyanurates form enantiotropic calamitic mesophases (nematic and in one case smectic). No discotic mesophases could be detected. The mesogenic power of the cyclotrimers is reversed with respect to that of the monomers from which they can be obtained (cyanates and isocyanates). Molecular calculations reveal that the cyanurates can adopt an extended rod-like conformation due to the flexibility introduced by the oxygen bridge between the central ring and the mesogenic branches. The direction of the ester group in the phenyl benzoate mesogenic branches has a tremendous influence on the mesomorphic properties, with the result that mesophases could only be observed if the benzoic acid part was attached to the triazine ring.     

Heterotrimeric liquid crystalline thiadiazole derivatives

Various trimeric co-oligomers combining 2-phenyl-1,3,4-thiadiazole mesogenic moieties with a biphenyl mesogenic moiety were synthesized and their mesomorphic behaviour investigated by polarizing microscopy, calorimetry and X-ray scattering. Such co-oligomeric structures provide an opportunity to combine different mesogenic units. Thus readily accessible homochiral biphenyl mesogenic units were connected with thiadiazole mesogenic units leading to an oligomeric liquid crystal material with ferroelectric properties.