Side chain liquid crystalline diethanolamine‐based polyesters with methoxy and/or nitroazobenzene mesogenic moieties

Side‐chain polyesters based on diethanolamine and 5‐hydroxyisophthalic acid with mesogenic methoxyazobenzene and nitroazobenzene groups were synthesized and their liquid crystalline properties were examined.

Four different types of polyesters were prepared by using various combinations of monomers differing in the mesogen group and the length of the spacer. The thermal and structural properties depend on the type of polyester as well as on the side chain length. The glass transition and isotropization temperatures increase when the methoxyazobenzene group is bound to a diol and decrease when it is bound to an isophthalic acid. Most of the polyesters are thermotropic liquid crystals and form a nematic phase on heating. Some polyesters exhibit shear induced isotropisation to nematic transition up to 25°C above the isotropization temperature.     

SYNTHESIS AND CHARACTERIZATION OF LIQUID CRYSTAL POLYESTERS WITH T-SHAPED TWO-DIMENSIONAL MESOGENIC UNITS(Ⅲ)*

A new series of liquid crystal polyesters with T-shaped two-dimensional mesogenic units weresynthesized by melt polycondensation of the diacetates of 2-(4'-alkoxy -phenyl)-hydroquinones with 4,4'-alkylenedioxydibenzoic acid. The polymers were characterized by using polarized microscopy, DSC and X-ray diffraction. It was realized that all the polymers have nematic thermotropic liquid crystallinecharacteristics. The melting temperature (T_m) and isotropization temperature (T_i) of the polymers changeregularly with varying lengths of the alkoxy side group and the length of the alkylene group in the main chainin company with an even-odd effect. The mesophase temperature range also varies regularly with the polymerstructure. It is shown that the mesophase range has been widened.     

Synthesis and mesophase characterization of liquid crystalline polyesters with bulky,rigid, lateral substituents

The synthesis and characterization of aromatic polyesters containing various symmetrically di-substituted hydroquinone monomers is described. The homopolyesters made from these monomers and terephthalic acid (TA) did not melt. Copolyesters of TA with mono- and di-substituted hydroquinone formed liquid crystalline melts. Optical microscopy showed schlieren, marbled, and droplet textures characteristic of the nematic phase. DSC experiments were also in accord with mesophase formation as multiple transitions characteristic of first-order phase changes were found. In general, the crystal-nematic transition was about 300°C, whereas the nematic-isotropic change was over 400°C. All the polyesters were prone to decomposition near or above the isotropization temperature. © 1994 John Wiley & Sons, Inc.     

Structure and mesophase of a new series of aromatic polyesters

A new series of aromatic polyesters in which the polymethylene flexible spacers are connected with the rigid main chain containing benzene ring were prepared by interfacial polycondensation. The polymers were characterized by hotstage polarized microscopy, differential scanning calorimetry, wide-angle X-ray diffraction and Fourier-transform infrared spectroscopy. The structure and properties of polyesters were investigated. The results showed that the textures of the thermotropic liquid-crystalline polyesters are smectic and/or nematic. The dependence of melting point, clearing point and transition enthalpy of polyesters on length of the alkylene group revealed a regular zig-zag trend. The thermal analysis of polyesters revealed that the clearing transition is an equilibrium process, so the entropy of this transition may be taken as an indication of the degree of the order in mesomorphic state presented in the system. Furthermore, the thermal history of polymer had a significant effect on its thermal behavior. The regular arrangement of methylene segments changed when polymer melted from the crystal state to the liquid-crystalline state. The research also implicated that the conformational change of the methylene flexible spacer was one of the reasons for this thermal effect.     

Dimer liquid crystals with bent mesogenic units

Three series of dimer liquid crystals containing an aromatic and a cholesteryl mesogenic unit were synthesized and investigated The compounds within the series differ in the length of the spacer connecting the mesogenic groups. Two of the three series contain an aromatic mesogenic group that is connected to the spacer at a meta-position instead of the para-position. Due to the presence of this bent mesogenic group, the odd-even effect in the transitional properties that is normally observed for dimer liquid crystals is reversed as compared with that of the third series, which contains a para-substituted aromatic mesogenic group. The reversed odd-even effect is found for the isotropization temperatures, the associated enthalpy changes and also for the optical properties.     

Fully aromatic thermotropic liquid crystalline polyesters of 3-phenyl-4,4′-biphenol with 4,4′-benzophenone dicarboxylic acid

A series of fully aromatic, thermotropic polyesters, derived from 3-phenyl-4,4′-biphenol (MPBP), nonlinear 4,4′-benzophenone dicarboxylic acid (4,4′-BDA), and various other comonomers was prepared by the melt polycondensation method and characterized for their thermotropic liquid crystalline behavior by a variety of experimental techniques. The homopolymer of MPBP with 4,4′-BDA had a fusion temperature (T_f) at 240°C, exhibited a nematic liquid crystalline phase, and had a narrow liquid crystalline range of 60°C. All of the copolyesters of MPBP with 4,4′-BDA and either 30 mol % 4-hydroxybenzoic acid (HBA), 6-hydroxy-2-naphthoic acid (HNA) or 50 mol % terephthalic acid (TA), 2,6-naphthale-nedicarboxylic acid (2,6-NDA) and low T_f values in the range of 210–230°C, exhibited a nematic phase, and had accessible isotropization transitions (T_i) in the range of 320–420°C, respectively. As expected, each of them had a broader range of liquid crystalline phase than the homopolymer. They had a “frozen” nematic, glassy order as determined with the wide-angle X-ray diffraction (WAXD) studies. The morphology of each of the “as-made” polyesters had a fibrous structure as determined with the scanning electron microscopy (SEM), which arises because of the liquid crystalline domains. Moreover, they had higher glass transition temperatures (T_g) in the range of 167–190°C than those of other liquid crystalline polyesters, and excellent thermal stabilities (T_d) in the range of 500–533°C, respectively. © 1995 John Wiley & Sons, Inc.     

Thermotropic liquid‐crystalline polymers having five‐membered heterocycles as mesogens, 3. New semi‐rigid thermotropic liquid‐crystalline polyesters based on a twin biphenyl analogue of 1,3,4‐thiadiazole

New semi‐rigid thermotropic liquid crystalline (LC) polyesters containing a twin biphenyl analogue of 1,3,4‐thiadiazole in the main chain were prepared by melt polycondensation of the bismethyl ester derivative of twin 2‐phenyl‐1,3,4‐thiadiazole having a decamethylene segment in the central part with three aliphatic diols. The polymer with an octamethylene segment forms a monotropic nematic phase and those with decamethylene and dodecamethylene segments form enantiotropic smectic phases, although their LC states are unstable. The melting and isotropization temperatures decrease with increasing length of alkylene spacers.     

Synthesis and characterization of new aromatic liquid crystalline polyesters having phenyl substituents

Two different series of new aromatic liquid crystalline (LC) polyesters were prepared from 3-phenyl-4, 4'-biphenyldicarboxylic acid (PBDA) and 1-phenyl-2, 6-naphthalenedicarboxylic acid (PNDA). PBDA and PNDA were polymerized with various aromatic diols such as hydroquinone, substituted hydroquinones, isomeric naphthalenediols and 4, 4'-biphenol, and the resulting polyesters were characterized by DSC, WAXD, and on a cross-polarizing microscope for the study of their thermal transition and crystallization properties, and mesophases formed therefrom.     

Dimeric liquid crystalline compounds having a central malonic acid moiety: effect of the length of the spacers and terminal chains

We have studied the liquid crystalline properties of two new series of dimeric compounds consisting of a central malonic acid moiety, polymethylene spacers, and Schiff's base mesogens. In the first series we changed the length of the spacers with the terminal chain fixed as the butoxy group; in the second series we changed the length of the terminal alkyl or alkoxy groups while keeping the spacers fixed as decamethylene groups. In the first series, as the length of the spacer increased, the tendency to form smectic phases grew. In the second series, changing the alkyl terminal chain to the alkoxy terminal group raised the melting and isotropization temperatures. Increasing the length of the terminal group diminished the temperature range for the higher temperature smectic phase. The smectic phases are assigned to be smectic A and crystal smectic E phases.     

Thermotropic liquid‐crystalline polyesters of 4,4′‐biphenol and phenyl‐substituted 4,4′‐biphenols with 4,4′‐oxybisbenzoic acid

A series of thermotropic polyesters, derived from 4,4′‐biphenol (BP), 3‐phenyl‐4,4′‐biphenol (MPBP), and 3,3′‐bis(phenyl)‐4,4′‐biphenol (DPBP), 4,4′‐oxybisbenzoic acid (4,4′‐OBBA), and other aromatic dicarboxylic acids as comonomers, were prepared by melt polycondensation and were characterized for their thermotropic liquid‐crystalline (LC) properties with a variety of experimental techniques. The homopolymer of BP with 4,4′‐OBBA and its copolymers with either 50 mol % terephthalic acid or 2,6‐naphthalenedicarboxylic acid had relatively high values of the crystal‐to‐nematic transition (448–460 °C), above which each of them formed a nematic LC phase. In contrast, the homopolymers of MPBP and DPBP had low fusion temperatures and low isotropization temperatures and formed nematic melts above the fusion temperatures. Each of these two polymers also exhibited two glass‐transition temperatures, which were associated with vitrified noncrystalline (amorphous) regions and vitrified LC domains, as obtained directly from melt polycondensation. As expected, they had higher glass‐transition temperatures (176–211 °C) than other LC polyesters and had excellent thermal stability (516–567 °C). The fluorescence properties of the homopolymer of DPBP with 4,4′‐OBBA, which was soluble in common organic solvents such as chloroform and tetrahydrofuran, were also included in this study. For example, it had an absorption spectrum (λ_max = 259 and 292 nm), an excitation spectrum (λ_ex = 258 and 292 nm with monitoring at 350 nm), and an emission spectrum (λ_em = 378 nm with excitation at 330 nm) in chloroform. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 141–155, 2002     

Synthesis, micro structure, and thermal stability of side chain liquid crystalline polysiloxane polymers with an oligo (ethylene oxide) unit in the side chain

A series of new alkene monomers [MS3BDBEn, n=1-3] containing 4-oligo (ethylene oxide) monomethyl ether 4-biphenyl ether carboxyl benzoate as terminal groups were synthesized. These polymers were prepared by grafting these monomers onto the poly (methylhydrosilox-ane) (PMHS) backbone. The transition temperatures, liquid crystalline textures, and thermal stability of the polysiloxane polymers have been determined by thermal data, by optical texture, and by X-ray diffraction patterns. Polymers PS3BDBEn showed smectic or smectic and nematic phases which were not analogous to their precursor nematic monomers. The terminal length of the polymers affects not only the mesophase transition temperatures but also the layer-spacing length (d₁) and the side-chain distance (d₂). The long- and short-range orders can remain to some extent above the isotropization temperature and below the melting point. The polymer PS3BDBE3 decomposed in air 20°C above the isotropization temperature and lost its short range orders as detected by the X-ray diffraction analysis.     

Dimeric liquid crystalline compounds having a central malonic acid moiety: effect of the length of the spacers and terminal chains

We have studied the liquid crystalline properties of two new series of dimeric compounds consisting of a central malonic acid moiety, polymethylene spacers, and Schiff's base mesogens. In the first series we changed the length of the spacers with the terminal chain fixed as the butoxy group; in the second series we changed the length of the terminal alkyl or alkoxy groups while keeping the spacers fixed as decamethylene groups. In the first series, as the length of the spacer increased, the tendency to form smectic phases grew. In the second series, changing the alkyl terminal chain to the alkoxy terminal group raised the melting and isotropization temperatures. Increasing the length of the terminal group diminished the temperature range for the higher temperature smectic phase. The smectic phases are assigned to be smectic A and crystal smectic E phases.     

Mesophase behaviour in fluorocarbon-hydrocarbon polyesters

A series of liquid crystalline main chain polyesters has been synthesized in which mesogenic, linear perfluoroalkyl groups are linked to aliphatic hydrocarbon chains. The liquid crystalline phase appears to be smectic B from X-ray diffraction data. Interesting differences in the mesophase transition temperatures and enthalpies are observed along the series, as the hydrocarbon and perfluoroalkyl contents are changed. These are discussed in relation to the length of the segments. One polymer was also synthesized from biphenyl-4,4'-dicarboxyic acid for comparison with the polyesters prepared using aliphatic dicarboxylic acids.     

Nematic and cholesteric thermotropic polyesters with azoxybenzene mesogenic units and flexible spacers in the main chain

Properties of linear polyesters based on azoxybenzene and 2,2′-methylazoxybenzene moieties with linear, flexible spacers based on mixtures of dodecanedioic acid (DDA) and methyladipic acid (MAA), chiral or racemic, of various compositions (system MAA/DDA-8 and MAA/DDA-9, respectively) have been described. Substitution of methyl groups in the 2,2′ or 3,3′ positions of the mesogenic core leads to soluble and relatively low-melting-point polyesters. The viscosity law for (MAA/DDA-9) polyesters in 1,1,2,2 tetrachloroethane gives an exponent 0.76, indicating well-sol-vated, coiled chain conformations in dilute solution. Calorimetric data show an increase in isotropization entropy ΔS_NI with increasing average length of the spacer. This suggests a nonrandom conformation of the spacer in the nematic melt with a degree of order superior to that of low-molecular-weight analogs. X-ray data obtained with an oriented nematic glass quenched from the nematic melt of DDA-9 subjected to a magnetic field of 10–12 T also support the extended-chain model in the nematic phase of DDA-9. Oriented fibers can be produced by subjecting nematic melts of polyesters 8 and 9 either to magnetic fields of high intensity or to shear fields. The x-ray data obtained from these fibers also support the extended-chain model. Cholesteric systems do not orient in the magnetic field of 10–12 T. The study of mesophases of systems 8 and 9 indicates a dramatic influence of the position of the ester group on the stability of the mesophase in the azoxybenzene polyesters. The results are interpreted in terms of geometric factors influencing the colinearity of the mesogenic core and of the extended spacer.     

Structure/property relationships for the thermotropic behavior of lysine-based amphiphiles: from hexagonal to smectic phases

Amino acid-derived gemini surfactants arise as a potentially good alternative to the more conventional lipid and synthetic catanionic systems in view of their enhanced interfacial properties, increased chemical stability, and low toxicity. The presence of an amino acid as the polar headgroup allows toxicity reduction, with the simultaneous increase of biodegradability. For these compounds, the establishment of structure/function relationships from the assessment of their basic aggregation properties is therefore of the utmost interest, e.g., in the design of operative self-assembled systems (e.g., liposomes, nanotubes, etc). In this context, the study of the thermal phase behavior of the dry surfactants is a natural, straightforward first step, the more so as thermotropic liquid crystals are also relevant for practical applications. In this work, several lysine-based amphiphiles with a gemini-like configuration have been synthesized, with the amino acid side chain as the spacer group. The molecules are either esters (neutral, with C6-C12 even chains) or sodium carboxylates (anionic, with C6-C12 even chains). Upon increasing the temperature, different crystalline (cr) and liquid-crystalline (lc) phases have been detected and the corresponding thermodynamic and structural parameters determined by a combination of differential scanning calorimetry, polarizing light microscopy and small-angle X-ray scattering. The phase behavior of the amphiphiles is highly dependent on both the chain length and the presence of charge on the headgroup, with significant differences occurring within and between each group of molecules. The C6 and C8 esters form reverse hexagonal cr and lc phases, while C10 and C12 self-assemble into smectic cr and lc structures, with C10 showing also a reverse hexagonal lc phase prior to isotropization. All the carboxylate derivatives form smectic lc phases at high enough temperature prior to isotropization. The rationalization of the phase behavior and phase transition energetics of the compounds has been put forth on the basis of the intermolecular interactions at stake (van der Waals, H-bonding, electrostatic, and packing) and the molecular shape of the amphiphile.     

Design,synthesis, and characterization of main‐chain,aromatic polyesters based on 3,4‐ethylenedioxythiophene

A series of new thermoplastic polyesters based on 3,4‐ethylenedioxythiophene (EDOT) with flexible aliphatic spacers have been synthesized and characterized for the first time. The thermal properties of these polyesters based on EDOT are comparable to those of conventional polyesters based on the 1,4‐phenyl unit, indicating that EDOT is a viable replacement for the phenyl units. The glass‐transition and melting‐transition temperatures decrease monotonically with an increase in the spacer length. Theoretical calculations have revealed that the core angle for EDOT is comparable to that of unsubstituted thiophene and hence should be compatible with the formation of the mesophase. This has been confirmed experimentally by the synthesis of a main‐chain, thermotropic, liquid‐crystalline polyester based on EDOT that exhibits fluid birefringence. In fact, this is the first report in which a main‐chain, liquid‐crystalline polymer based on 3,4‐disubstituted thiophene has been successfully designed and synthesized. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3479–3486, 2006     

Dimer liquid crystals with bent mesogenic units

Three series of dimer liquid crystals containing an aromatic and a cholesteryl mesogenic unit were synthesized and investigated The compounds within the series differ in the length of the spacer connecting the mesogenic groups. Two of the three series contain an aromatic mesogenic group that is connected to the spacer at a meta-position instead of the para-position. Due to the presence of this bent mesogenic group, the odd-even effect in the transitional properties that is normally observed for dimer liquid crystals is reversed as compared with that of the third series, which contains a para-substituted aromatic mesogenic group. The reversed odd-even effect is found for the isotropization temperatures, the associated enthalpy changes and also for the optical properties.     

Laterally linked mesogens in main chain polymers

The syntheses of liquid-crystalline main chain polyesters with laterally linked mesogens are presented. The terminal groups of the mesogens and the spacers fixation of mesogens, the polyesters with 1,4-di(p-alkoxybenzoyloxy)benzenes 1,4-di(p-alkoxybenzolyloxy)benzenes, 2,5-di(p-alkoxyphenyl)pyrimidines or a 4,4'-bis(p-ethoxyphenylazo)biphenyl derivative. Despite the unusual bilateral fixation of mesogens, the polyesters with 1,4-di(p-alkoxybenzoyloxy)benzenes show mainly monotropic phases which were found to be nematic in investigations with the polarizing microscope, in DSC measurements, temperature-dependent measurements of the Kerr constant and X-ray diffraction experiments. The monotropic nematic character remains when varying the terminal groups of the mesogen as well as the length of the n-alkanedioic acid spacer. However, when the spacer is branched, crystallization can be disturbed effectively and a stable nematic phase can be obtained. All of the polyesters with only 2,5-di(p-alkoxyphenyl)-pyrimidines as mesogens are amorphous. The reason probably lies in the unsymmetric 4,6-substitution of the pyrimidine ring. In contrast to this, oligomers with a 4,4'-bis(p-ethoxyphenylazo)biphenyl derivative show broad, predominantly enantiotropic nematic phases with relatively high clearing temperatures. With the knowledge gained about relations between structure and properties, especially of polyesters with 1,4-(p-alkoxybenzoyloxy)benzenes as mesogens, polyesters with this mesogenic group but with various architectures have been compared. Speculations about possible arrangements of the structural elements have been included to explain the phase behaviour of the polyesters with laterally fixed mesogens.     

Patterned retarders prepared by photoisomerization and photopolymerization of liquid crystalline films

Isomerizable diacrylates derived from cinnamic acid are designed, synthesized and mixed with liquid crystalline diacrylates with the aim of making films with alternating birefringent and isotropic domains by applying the E-Z isomerization process at room temperature. The effects of the structure of the isomerizable-mesogenic group on the isotropization efficacy, the efficiency of the E-Z isomerization reaction, and film formation are discussed. Compounds derived from cyclohexyl cinnamate are proved to be good candidates that meet a whole set of parameters related to processing and application. These compounds exhibit a low nematic-to-isotropic transition temperature. In addition, they show no yellowing upon irradiation, unlike similar compounds derived from phenyl cinnamate. To elucidate the origin of isotropization of the film by irradiation, the pure Z-isomer is prepared by photolysis of the E-isomer and subsequent chromatographic separation of both isomers. Analysis of reference samples containing the pure isomers reveals that the decrease in transition temperature can be attributed exclusively to the E-Z photoisomerization process. Finally, thin films with alternating birefringent and isotropic parts of 100×100 µm² are obtained by using a combination of photoisomerization in air and photopolymerization in a nitrogen atmosphere, which is referred to as photo-patterning.     

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.