Oligo ( p -phenylene)s substituted with long alkoxy chains I. Thermotropic liquid crystalline properties and UV absorption/emission characteristics

A series of linear oligo ( p -phenylene)s containing three, five and seven phenylene groups, modified with short lateral and long terminal alkoxy chains, were synthesized via Palladium complex-catalysed cross-coupling reactions. The thermotropic liquid crystalline and UV absorption/emission properties of these compounds were studied. It was observed that tri ( p -phenylene)s develop a rich mesomorphism including tilted smectic type mesophases (SmC and SmF/SmI) and the nematic phase, whereas penta- and hepta-( p -phenylene)s substituted with short lateral chains develop only the nematic phase. From these observations it is clear that the short lateral chains hinder the layered molecular packing typical of smectic phases and promote the formation of the less ordered liquid-like nematic phase. Mesophases appeared at lower temperatures when longer end chains were used. The optical properties studied by UV-Vis and emission spectroscopy indicate that these systems are promising candidates for blue-emitting layers in electroluminescent devices.     

Studies on thermotropic liquid crystalline polymers. XIV. Synthesis and properties of liquid crystalline poly(imide-ester)s by the direct polycondensation

A series of semi-aromatic poly(imide-ester)s were prepared by the direct polycondensation of N-(4-carboxyphenyl) trimellitimide or N-(3-carboxyphenyl) trimellitimide with various pyromellitic diimide diols containing methylene spacer = 2–6, respectively. The effect of the amount of LiCl, pyridine, and the kinds of condensation agents on the direct polycondensation were studied. The structures and thermal properties of the synthesized poly(imide-ester)s were examined by FTIR spectrum, wide-angle x-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermal optical polarized microscopic observation, and thermogravimetric analysis (TGA). It is found that P1 series [derived from N-(4-carboxyphenyl) trimellitimide] with even number methylene spacer (n = 4, 6) exhibit smectic mesophase, but P2 series [derived from N-(3-carboxyphenyl) trimellitimide] do not show LC phase. © 1996 John Wiley & Sons, Inc.     

Synthesis and properties of liquid crystalline polyurethanes

1,4-Bis(p-hydroxybenzoate)phenylene was prepared using 1,4-bis(trimethylsiloxy)benzene and p-hydroxybenzoyl chloride as starting materials. A series of novel 1,4-bis(p-hydroxyalkoxybenzoate)phenylene were synthesized by reaction of 1,4-bis(p-hydroxybenzoate) phenylene with 3-brompropanol and 4-bromobutanol, respectively. The liquid crystal polyurethanes were prepared by 1,4-bis(p-hydroxyalkoxybenzoate)phenylene with MDI (p-methylene diphenylenediisocyanate) and 2,4-TDI(2,4-toluenediisocyanate), respectively. The thermotropic properties, the melting point (T _m) and the isotropization temperature (T _i) of the synthesized polyurethanes were characterized by DSC, IR and POM. It showed that all of the polyurethane polymers exhibited thermotropic liquid crystalline properties between 144°C and 260°C. The transition temperature (T _m and T _i) decreased with an increase in the length of the methylene spacer. __________ Translated from Journal of Qingdao University of Science and Technology, 2006, 27(1) (in Chinese)     

New symmetric azobenzene molecules of varied central cores: Synthesis and characterisation for liquid crystalline properties

A new series of azobenezene liquid crystals (LCs) was designed and synthesised by known and straightforward methods. The central connecting cores of the molecules varied viz., benzene/naphthalene/biphenyl. The molecular structures were confirmed by infrared, UV, nuclear magnetic resonance spectroscopic techniques. The LC texture and thermal phase behaviours were investigated by polarising optical microscopy and differential scanning calorimetry. Smectic B phase was found in biphenyl-derived azobenzene ester. The effect of central core on LC properties was investigated. The decreased angle at central connecting core suppressed the melting points, phase transition temperatures without losing LC properties, whereas, in moderate angle compounds LC properties were suppressed. The compounds with increased angle at central core favours rich mesomorphism.     

Study on the thermotropic liquid crystalline polycarbonates. IV. Synthesis and properties of liquid crystalline poly(imide-carbonate)s

Two series of novel thermotropic liquid crystalline poly(imide-carbonate)s were prepared by melt polycondensation from various arylene or alkylene bis(phenylcarbonate)s by using N,N′-bis(hydroxyethyl)pyromellitimide and N,N′-bis(hydroxypropyl)pyromellitimide as monomers. Thermotropic liquid crystalline properties were characterized by a polarizing microscope with a heating stage and a differential scanning calorimeter (DSC). Nematic melts were found for the synthesized aromatic poly(imide-carbonate)s. In order to investigate whether the pyromellitimide unit could be used as a mesogenic unit for preparing LC polymers, a series of aliphatic poly(imide-carbonate)s was prepared in this study. However, no significant LC textures were found under the observation by polarizing microscope. It was suggested that the aspect ratio of the pyromellitimide unit was too short to form liquid crystalline poly(imide-carbonate)s. In addition, it was interesting that the aliphatic poly(imide-carbonate)s with a longer spacer (n = 3) in the pyromellitimide unit showed better crystallinity. Thermostabilities of all synthesized poly(imide-carbonate)s were measured by thermogravimetric analysis (TGA). © 1994 John Wiley & Sons, Inc.     

Liquid crystalline polymers V. Thermotropic liquid crystalline poly(azomethine-ether)s containing a cycloalkanone moiety in the polymer backbone

A new homologous series of thermotropic liquid crystalline poly(azomethine-ether)s was synthesized by solution polycondensation of various diformyl-alpha,omega-diphenoxyalkanes, I-VIII with 2,5-bis(m-aminobenzylidene)cyclopentanone, XI and 2,6-bis(m-aminobenzylidene)cyclohexanone, XII. The inherent viscosities of the polymers were in the range 0.34-0.75 dI g^-1. The mesomorphic properties were studied as a function of the diphenoxyalkane spacer length. Analyses by DSC and optical polarized microscopy demonstrated that the poly(azomethine-ether)s form nematic mesophases over wide temperature ranges. The poly(azomethine-ether)s based on the cyclohexanone moiety had better thermal stabilities than the corresponding poly(azomethine-ether)s based on cyclopentanone.     

Thermotropic liquid-crystalline properties of extended viologen bis(triflimide) salts

A series of extended, symmetric viologen triflimides were synthesised by the metathesis reaction of lithium triflimide with the respective viologen tosyalates in methanol. Their chemical structures were characterised by Fourier Transform Infrared, ¹H and ¹³C Nuclear Magnetic Resonance spectroscopy and elemental analysis. Their thermotropic liquid-crystalline (LC) properties were examined by a number of experimental techniques including differential scanning calorimetry, thermogravimetric analysis, polarising optical microscopy and variable temperature X-ray diffraction. The viologen salts containing alkyl chain of two carbon and three carbon atoms were relatively low melting salts. Those of alkyl chains of four carbon and five carbon atoms formed ionic liquids at 88 and 42°C, respectively. Those of alkyl chain of 9, 10 and 11 carbon atoms were high melting salts, as high as 166°C. Those of higher alkyl chains of 16, 18 and 20 carbon atoms showed thermotropic LC phases forming SmC, SmA and an unidentified smectic (SmX) phases, and showed SmA to isotropic transitions at high temperatures. As expected, all the viologen triflimides had excellent stabilities in the temperature range of 338–365°C.     

Synthesis and characterization of novel thermotropic liquid crystalline copoly(ester imide)s

Novel liquid crystalline copoly(ester imide)s were synthesized via polyesterification of triethyleneglycol bis(4-carboxyphenyl) ether ( 1e ), diacetoxybiphenyl, and diacids with imide moieties. The effects of composition on the changes of T_g, T_m, and T_i were examined by global TSC and DSC. Thermal gravimetric analyses (TGA) found that 4a–d and 5a–g possess higher thermal stability. Strong stir opalescence phenomenon and observations from polarized optical microscopy identified that 2b–e and 3a–d possess the typical schlieren texture of an enantiotropic nematic mesophase. The birefrigent melts of 4a–d and 5a–g, however, displayed particular liquid crystalline behavior. Copolymers with higher aromatic imide ring content ( 4a–d, 5a–g ) form a layered structure and an enantiotropic smectic mesophase in the melting state. The melt viscosity of the semetic mesophase was higher than the nematic mesophase which was observed by capillary rheometer. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1791–1803, 1998     

Studies on thermotropic liquid crystalline polymers. XV. Synthesis and properties of liquid crystalline copoly(imide-ester)s

Three series of the thermotropic liquid crystalline copoly(imide-ester)s were prepared by direct polycondensation. The first two series of the copoly(imide-ester)s were synthesized from N-(4-carboxyphenyl) trimellitimide with N,N-di(hydroxypropyl) pyromellitic diimide and various aromatic diols. The third series of copoly(imide-ester)s were prepared by N-(4-carboxyphenyl) trimellitimide with various imide-diols (methylene spacer = 2–6) and phenyl hydroquinone. The structures and thermal properties of the synthesized poly(imide-ester)s were examined by FTIR spectrum, wide-angle x-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermal optical polarized microscope, and thermogravimetric analysis (TGA). The effects of the structures of the aromatic diols on the thermal properties of the resulting copoly(imide-ester)s were investigated. It was found that most of the copoly(imide-ester)s possessed excellent mesophase stabilities and thermostabilities. The mesophase stabilities of poly(imide-ester)s decreased with the increase of the size of lateral group, and the mesophase range increased with the increase of the amount of PhHQ. No significant odd-even effects were observed between the methylene spacer lengths and transition temperatures. © 1996 John Wiley & Sons, Inc.     

Synthesis and mesomorphic properties of four ring,rod-like fluorene derivatives – the influence of the lateral substitution on mesomorphic properties of 2,7-bis(4-alkylphenyl)-fluorenes

ABSTRACT

This work presents new rod-like compounds being fluorene derivatives linked with other parts of the core at 2 and 7 positions – its synthesis and properties. The fluorene moiety is located in the central position of the four rings molecular core. The chain system in most cases was symmetrical and limited to pentyl or hexyl chains. To study the influence of the lateral substituents on mesomorphic properties two types of substituents have been incorporated, centrally located various short alkyl groups at fluorene’s 9,9 positions and outer core fluorosubstitutions located at side phenyl rings. All synthesised compounds exhibit liquid crystalline properties, where for laterally non-substituted and fluorosubstituted derivatives the dominant phases are smectics, while the nematics phases (nematic and chiral nematic – observed mostly on cooling cycle) occurs for compounds having alkyl substituents at 9,9 positions of fluorene. The synthetic methodology and mesomorphic properties of title compounds will be presented in detail as well as photophysical properties such as UV-visible absorption spectra and fluorescence spectra.     

Synthesis and liquid crystalline investigation of chiral 6-alkoxy-2-naphathoic acid derivatives

A two new series of materials with a chiral fragment derived from ((S)-(─)-2-methyl-1-butanol and 6-alkoxy-2-naphathoic acid as the molecular core was synthesised and investigated. All the homologues exhibited enantiotropic mesomorphism. Chiral smectic C (SmC*), smectic A (SmA) and chiral nematic (N*) phases were observed in different homologues. All the compounds were characterised by spectroscopic and elemental analysis. Thermal investigations and mesophase characterisations for all the compounds were carried out by the combination of DSC and POM analysis. The effects of the central linkage and various terminal normal alkyl chains with its structurally related compounds have been discussed.     

Thermotropic liquid crystalline polymers with low thermal transitions. II. Low melting thermotropic liquid crystalline homo- and co-polyesters

Thermotropic liquid crystalline (TLC) polymers with low melt transitions are useful for imaging technologies. This is the first report describing thermotropic liquid crystalline copolyesters of low melt transitions comprised of a mesogen with up to three different spacer moieties. We have noted that the smectic mesophase range decreased with increasing amounts of different spacer moieties, without altering the isotropic transition and thereby leading to a broader nematic range. © 1995 John Wiley & Sons, Inc.     

Liquid crystalline main chain polymers with a poly(p-phenyleneterephthalate) backbone. 2. Fiber spinning and mechanical properties of polyesters with alkoxy side chains

Fiber spinning and mechanical properties of four rigid polyesters with alkoxy substituents of different length and placement were evaluated. Properties of oriented fibers from the polymer with dodecyloxy substituents on the terephthalate moiety, PTA12HQ, were significantly affected by the crystal modification. At room temperature the following properties (tensile modulus E, tensile strength σ_b, and strain at break ε_b) could be obtained: E = 9.5 GPa, σ_b = 85 MPa and ε_b = 1.1% for phase L_f (the “frozen in layered mesophase”); E = 10.4 GPa, σ_b = 59 MPa and ε_b = 0.6% for modification A; E = 17.3 GPa, σ_b = 158 MPa and ε_b = 1.2% for modification B. Because of the higher amount of main chains per cross sectional area the polymer with hexyloxy side chains, PTA6HQ, showed better properties at a comparable degree of molecular orientation: E = 24 GPa, σ_b = 270 MPa, ε_b = 1.4%. Fibers obtained from the polyester with dodecyloxy substituents on the hydroquinone moiety, PTAHQ12, were too brittle to handle. The polyester with dodecyloxy substituents on both moieties, PTA12HQ12, was spun from the isotropic melt. Because of the obtained low degree of orientation, properties (E = 1 GPa, σ_b = 40 MPa, and ε_b = 6.3%) were governed by interactions between the chains (the main chains are not load-bearing). © 1993 John Wiley & Sons, Inc.     

Synthesis,phase transitions and birefringence of novel liquid crystalline 1,4-phenylene bis(4-alkylthio benzoates) and insights into the cybotactic nematic behaviour

We synthesised a novel family of liquid crystalline 1,4-phenylene bis(4-alkylthio benzoates), of which homologues with different alkyl chain lengths of 1–8 were designed, to investigate the structure–property relationship. The mesogenic incidence and tendency were found to be strongly dependent on the carbon numbers in the terminal alkyl chains. Even members formed widely monotropic or enantiotropic nematic (N) phases compared to odd members that showed either none or monotropic-narrower ones. The temperature dependence of birefringence (Δn) for the hexylthio homologue was evaluated and compared to that for a hexyloxy counterpart. It was found that the hexylthio homologue exhibited higher Δn values than the hexyloxy counterpart over the entire range of near T_IN–T. In addition, wide-angle X-ray diffraction measurements, using magnetically aligned specimens, found enhanced cybotactic nematic tendency with smectic (Sm) A-like temperature dependence for the hexylthio analogue, due to the intermolecular attractive S···S interaction, in comparison with the hexyloxy analogue exhibiting N phase with clear Sm C-type clusters. We revealed the actual benefits of alkylthio groups in the fluid N phase.     

Thermotropic liquid‐crystalline poly(oxadiazole)s with poly(methylene) spacers: Preparation and extraordinary odd–even effect

A novel synthetic procedure for the preparation of poly(oxadiazole)s was developed with nucleophilic substitution of α,ω-alkanediols with oxadiazole-activated bisfluoride. Seven poly(oxadiazole)s were successfully prepared by the solution polymerization of 2,5-bis(4-fluorophenyl)-1,3,4-oxadiazole and various α,ω-alkanediols [HO (CH₂)_n OH, n = 5–10 or 12] in diphenyl sulfone at temperature greater than 230 °C with K₂CO₃ as a catalyst. The reduced viscosities of the poly(oxadiazole)s were 0.14–0.51 dL/g, and the decomposition temperatures were greater than 350 °C and decreased from 436 to 379 °C with increasing spacer length (n). Corresponding model compounds, consisting of two terminal mesogenic 2,5-bisphenyl-1,3,4-oxadiazole units and central poly(methylene) spacers, were also prepared for comparison. Both the polymers and model compounds exhibited an extraordinary odd–even effect: odd ones showed higher transition temperatures (melting and clearing temperatures). With differential scanning calorimetry, polarized optical microscopy (POM), and X-ray diffraction, we found that the nematic mesophase was the only texture in the melts except for the polymers with longer methylene units (n = 9), in which smectic mesophases were observed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 293–301, 2002     

Studies on thermotropic liquid crystalline elastomers. II. Synthesis and properties of liquid crystalline polyester elastomers

Three series of novel thermotropic liquid crystalline polyester elastomers (TLCPEEs) were prepared by direct polycondensation from terephthalic acid, polyols (M_n = 1000 or 2000), and various diols. The structures and thermal properties of the synthesized TLCPEEs were examined by FTIR spectroscopy, differential scanning calorimetry, thermal optical polarized microscopy, thermogravimetric analysis, and wide-angle x-ray diffraction. The effects of kinds and amount of diols and the molecular weight of polyols on the thermal properties of TLCPEEs were studied. By introducing long flexible spacers (PE-1000 or PE-2000) into the polymer main chain, all polymers showed two-phase morphology under the thermal optical microscopic observation. All of the synthesized polymers, except polymer P1-BPA60 and P2-BPA60, which were prepared from BPA, exhibited thermotropic liquid crystalline properties that were in the smectic phase. © 1995 John Wiley & Sons, Inc.     

Liquid crystalline polymers XVI*. Thermotropic liquid crystalline copoly(arylidene-ether)/TiO2 Nanocomposites: synthesis,characterisation and applications

ABSTRACT

Polymer nanocomposites are already a part of many important worldwide businesses. Among many nanocomposite precursors, titanium dioxide (TiO₂) nanopowder is increasingly being investigated due to its special properties. In this work, the feasibility of synthesising a new series of materials, copoly(arylidene-ether)/titanium dioxide nanocomposites, using in-situ copolymerisation technique has been investigated. This can be performed by the interaction of both cyclohexanone and 4-tert-butylcyclohexanone monomers with 4,4′-diformyl-2,2′-dimethoxy-α,ω-diphenoxyalkanes Ia–e, respectively, using different additions of titanium dioxide-P25. The structure of the prepared nanocomposites IIa–e/TiO₂ (0.2–3.0%) was confirmed by elemental analysis (energy dispersive X-ray spectroscopy) and spectral data (Fourier transform-infrared [FT-IR]). FT-IR verified the dispersion of nanofillers in the copolymer. Then, the characterisation and applications of these nanocomposites are extensively discussed depending on the investigation of how the addition of titanium dioxide nanoparticles affected on their properties using various techniques, such as X-ray diffraction, SEM, transmission electron microscopy, Water Contact Angle (WCA), thermogravimetric analysis, differential thermogravimetric, differential thermal analysis (DTA), polarising optical microscope and UV–vis absorption spectroscopy. The nanoparticles affected on the copolymer thermal behaviour in different ways (discrepancy results) depending on how these nanoparticles are dispersed in the copolymer matrix. UV–vis absorption spectra displayed a decrease in the optical band gap of some nanocomposites, which resulted from the addition of titanium dioxide to these copolymers, and this can improve the efficiency of them as organic emitting materials.     

Liquid crystalline properties of penta(p-phenylene)s modified with short lateral and long terminal alkoxy chains

A series of penta(p-phenylene)s modified with short and long alkoxy groups was synthesized via palladium complex-catalysed cross-coupling reactions. Molecules substituted with butoxy groups in the central ring showed a nematic phase characterized by a schlieren optical texture, whereas those molecules lacking lateral groups, or substituted with shorter than butoxy groups, did not exhibit liquid crystallinity. Also, it was determined that both the mesophase stability and the clearing point were strongly dependent on the length of the terminal chains. Finally, optical studies of these compounds indicated that the observed light absorption/emission characteristics are independent of the chain lengths.     

Mesomorphic phase transitions and electro-optical properties of benzyl fluoroalkyl thioether liquid crystalline compounds

Four series of liquid crystalline (LC) compounds containing benzyl perfluoroalkyl thioether groups (BFT), 4-n-alkoxyphenylbenzyl perfluoroalkyl thioethers (nO-BBFT-FmF), 4-n-alkoxyphenylbenzyl perfluoroisoalkyl thioethers (nO-BBFT-FmIF), 4-n-propylcyclohexylbenzyl perfluoroalkyl thioethers (3-C1BFT-FmF) and 4-ethylcyclohexyl-3'-fluorobenzyl perfluoroalkyl thioethers (2-C1FBFT-FmF), were synthesized and their mesomorphic phase transitions and electro-optical properties investigated. nO-BBFT-FmF and nO-BBFT-FmIF have SmA, SmB and CrE phases, while 3-C1BFT-FmF and 2-C1FBFT-FmF showed a SmB phase. It was found that the appearance of a LC phase and the thermal stability were closely connected with the chemical structures of the rigid core part and the terminal groups. The electrooptical properties were investigated for BFT using ZLI-1132 as nematic solvent. Some of the BFT compounds have a good solubility of 15 wt % in ZLI-1132 and can be used as a component for lowering the refractive anisotropy (Delta n) of the host ZLI-1132 solvent.     

Studies on thermotropic liquid crystalline elastomers. I. Synthesis and properties of poly (amide-ester) elastomers

Three series of novel poly(amide-ester) (PAE) elastomers were prepared by direct poly-condensation from terephthalic acid (TPA), polyols (M_n = 1000 or 2000), and various diamines. The structures and thermal properties of the synthesized PAEs were examined by FTIR spectroscopy, wide angle X-ray diffraction (WAXD), differential scanning calo-rimetry (DSC), thermal optical polarized microscopy, thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). The effects of kinds and amount of diamines and the molecular weight of polyols on the thermal properties of PAEs were studied. By introducing long flexible spacers (PE-1000 or PE-2000) into the polymer main chain, all polymers showed two-phase morphology under the thermal optical microscopic observation. It was interesting that most of the synthesized polymers exhibited only one melting transition corresponding to the soft segments. The melting transition of hard segments could not be detected due to decomposition of the soft segments. However, a thermotropic liquid crystalline PAE (TLCPAE) prepared from methylhydroquinone and 2-chloro-5-methyl-phenylenediamine with PE-1000 could be obtained by lowering the melting transition temperature of the hard segment. © 1995 John Wiley & Sons, Inc.