Synthesis and thermotropic liquid crystalline behaviour of novel poly(aryl ether ketone)s with a lateral methoxy group

Novel poly(aryl ether ketone)s containing a lateral methoxy group were synthesized by nucleophilic substitution reactions of 4,4'-biphenol and methoxyhydroquinone with 1,4-bis(4-fluorobenzoyl)benzene in a sulfolane solvent in the presence of anhydrous potassium carbonate. Their thermotropic liquid crystalline properties were characterized by a variety of experimental techniques, e.g. differential scanning calorimetry (DSC), polarized light microscopy and temperature-dependent FTIR. Thermotropic liquid crystalline behaviour was observed in the copolymers containing 30-80 mol-% mexthoxyhydroquinone. Both melting (T-m) and isotropization (T-i) transitions appeared in the DSC curves. The polarized light microscopy study of the liquid crystalline copolymers suggested their ordered smectic structures. As expected, the copolymers had lower melting transitions than the biphenol-based homopoly(aryl ether ketone)s because of the copolymerization effect of the crystal-disrupting monomer methoxyhydroquinone.

Shear-induced spiral-like morphology of a main-chain liquid crystalline poly(aryl ether ketone)

The shear-induced spiral-like morphology of a main-chain thermotropic liquid crystalline poly(aryl ether ketone) is observed and characterized by means of polarizing light microscopy, atomic force microscopy, transmission electron microscopy and electron diffraction techniques. The spiral-like texture is formed during shearing in the temperature range of liquid crystalline to isotropic transition (335-340 degreesC), and dispersed discontinuously in the mosaic matrix. Electron diffraction results indicate that the spiral exhibits orthorhombic lateral packing of the crystals and homeotropic alignment of the molecules. The spiral formation process and possible affecting factors are discussed.

Homoepitaxial crystallization in films of a thermotropic liquid crystalline chloro-poly(aryl ether ketone)

The homoepitaxial crystallization in the films of a thermotropic liquid crystalline chloro-ply(aryl ether ketone) is studied by transmission electron microscopy (TEM) and electron diffraction (ED). The homoepitaxy takes place in the temperature range 330-320 degreesC, in which a highly-ordered smectic crystalline phase of the copolymer with a single-crystal-like banded structure is formed during the cooling process from the isotropic melt. The homoepitaxial crystallizations with angles of 32 degrees and 122 degrees between the two b axes are the major populations observed, and possess epitaxial contact planes of (100)(I)-(210)(II) and (010)(I)-(210)(II); respectively.

Study on a series of main-chain liquid-crystalline ionomers containing sulfonate groups

A series of main-chain Liquid-crystalline ionomers containing sulfonate groups pendant on the polymer backbone were synthesized by an interfacial condensation reaction of 4,4'-dihydroxy-alpha,alpha'-dimethyl benzalazine, a mesogenic monomer, with brilliant yellow (BY), a sulfonate-containing monomer, and a 1/9 mixture of terephthaloyl and sebacoyl dichloride. The structures of the polymers were characterized by LR and UV spectroscopies. DSC and thermogravimetric analysis were used to measure the thermal properties of those polymers, and the mesogenic properties were characterized by a polarized optical microscope, DSC, and wide-angle X-ray diffraction. The ionomers were thermally stable to about 310 degreesC. They were thermotropic liquid-crystalline polymers (LCPs) with high mesomorphic-phase transition temperatures and exhibited broad nematic mesogenic regions of 160-170 degreesC, and they were lyotropic LCPs with willowy leaf-shaped textures in sulfuric acid. However, the thermotropic liquid-crystalline properties were somewhat weakened because the concentration of BY was more than 8%. The inherent viscosity in N-methyl-2-pyrrolidone suggested that intramolecular associations of sulfonate groups occurred at low concentration, and intermolecular associations predominated at higher concentration. (C) 2001 John Wiley & Sons, Inc.

Molecular and supramolecular deformations and disclinations in a liquid crystalline copolyether thin films under an electrostatic field

An alignment study of a liquid crystalline copolyether TPP-7/11(5/5) thin films has been carried out in a 10 kV . cm(-1) electrostatic field parallel to the thin film surface normal. This copolyether possesses a negative dielectric anisotropy. The chain molecules are homogeneously aligned in the electric field and they form two-dimensionally ordered lamellae in a tilted columnar phase when the samples were cooled to room temperature. It is observed that the chain molecules are splayed to form bent lamellae and the chain direction is perpendicular to the tangential direction of the lamellar surfaces. These lamellae thus become replicas of the chain orientation, Due to the flexoelectric effect and density fluctuation on the thin film free surface, disclinations having topological strength s = 1, c = pi /4 and defect walls form. These s = 1 disclinations possesses both left- and right-handednesses. Discussion of the defect formations have been attempted.

Synthesis and characterization of chiral smectic side-chain liquid crystalline polysiloxanes and ionomers containing sulfonic acid groups

The synthesis of new chiral smectic A (S-A) side-chain liquid crystalline polysiloxanes (LCPs) and ionomers (LCIs) containing 4-allyloxy-benzoyl-4-(S-2-ethylhexanoyl) p-benzenediol his ate (ABB) as mesogenic units and 4-[[4-(2-propenyloxy)phenyl] azo]benzensulfonic acid (AABS) as nonmesogenic units is presented. The chemical structures of the monomers and polymers are confirmed by FTIR spectroscopy or H-1-NMR. Differential scanning calorimetry (DSC), optical polarizing microscopy, and X-ray diffraction measurements reveal that all the polymers P-I-P-IV and ionomers P-V-P-VI exhibit S-A texture. The results seem to demonstrate that the tendency toward the S-A-phase region increases with increasing sulfonic acid concentration, and the thermal stability of the S-A phase is determined by the flexibility of the polymer backbones and the interactions of sulfonic acid groups. (C) 2001 John Wiley & Sons, Inc.

Studies on the structure and properties of thermotropic liquid crystalline poly(aryl ether ketone)s

Series of thermotropic liquid crystalline poly (aryl ether ketone) s were synthesized by mucleophilic substitution reactions of 4,4'-biphenol and substituted hydroquinone with different difluoromonomers, The relationship between structure and properties of the novel copolymers was investigated. For the copolymers with liquid crystalline properties, their melting transition temperatures show no great change with increase the content of the crystal-disrupting unit. The reason is that the crystal phase is directly transformed from the ordered liquid crystal phase. Side-groups have important effect on mesophase stability, The temperature range of mesophase stability for the chloro-polymers is smaller than those of other series of copolymers (P-phenyl, t-butyl, methoxy, 3-trifluoromethylbenzene). This behavior indicates that the effect of geometric repulsive factor on the thermodynamic stability of the mesophase is much larger than that of the polarizability attractive factor. Different ordered liquid crystal phases are observed in the polymers with different molecular weights. At low molecular weight, highly ordered smectic liquid crystal phases form. With increasing the molecular weight, the ordered degree of the liquid crystals decreases, and only the nematic liquid crystal phase is observed in the polymer with higher molecular weight.

Electrostatic-field-induced chain alignment of liquid crystalline copolyether TPP thin films

A liquid crystalline (LC) copolyether has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,11-dibromoundecane with a 50/50 (both in %) equal composition of the 7- and 11-methylene monomers [coTPP-7/11(5/5)]. A mono-domain with a homeotropic alignment can be induced by a thin film surface in the LC phase. When an electrostatic field is applied to the surface-induced mono-domains parallel to the thin film surface normal, the molecular alignment undergoes a change from the homeotropic to uniaxial homogeneous arrangement. However, when the field is applied to a direction perpendicular to the thin film surface normal. the molecular alignment is about 10 degrees -tilt with respect to the homeotropic alignment toward the a*-axis. This is because the permanent dipole moment of the copolyether is not right vertical to the molecular direction. The calculation of molecular dipoles indicates that the permanent dipole moment of this copolyether is about 70 degrees away from the molecular axis, which leads to a negative dielectric anisotropy. It is speculated that the 10 degrees- rather than 20 degrees -tilt is due to a balance between the alignment induced by the electrostatic field and the surface. In the electrostatic field, molecules are subjected to a torque tau, which is determined by the permanent dipole moment P and the electrostatic field E: tau = P x E. The molecular realignment in both parallel and perpendicular directions to the thin film surface normal is determined by satisfying the condition of tau = P x E = 0. (C) 2001 Elsevier Science Ltd. All rights reserved.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 7. Phase structures in a series of copolyethers containing odd and even numbers of methylene units of different compositions

A series of liquid crystalline copolyethers have been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,12-dibromododecene [coTPPs(7/12)], which represents copolyethers containing both odd and even numbers of methylene units. The molar ratio of odd to even methylene units in this series ranges from 1/9 to 9/1. The coTPPs(7/12) exhibit multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. For all these thermal transitions, a small undercooling and superheating dependence is observed upon cooling and heating at different rates. Three types of phase behaviors can be classified in coTPPs(7/12) on the basis of the structural analyses by wide-angle X-ray diffraction on powder and fiber samples and by electron diffraction experiments in transmission electron microscopy. At room temperature, highly ordered smectic and smectic crystal (SC) phases are identified in coTPPs(7/12: 1/9 and 2/8), which is similar to the homopolymer TPP(m = 12). The coTPPs(7/12: 3/7, 4/6, and 5/5) possess a hexagonal columnar (Phi(H)) phase in which the molecular and columnar axes are parallel to the fiber direction and perpendicular to the hexagonal lateral packing. The coTPPs(7/12: 6/4, 7/3, and 8/2) possess a tilted hexagonal columnar (Phi(TH)) phase with a single tilt angle which increases with the increasing composition of the seven-numbered methylene units. However, in coTPP(7/12: 9/1), a Phi(TH) phase with multiple tilt angles is found. Upon heating, phase structures in most coTPPs(7/12) involving the columnar phases enter directly into the nematic (N) phase, while the coTPP(7/12: 1/9) exhibits a highly ordered smectic F (S-F) phase before it reaches the N phase. One exception is found in coTPP(7/12: 2/8), wherein the transformation from the S-F to Phi(H) occurs prior to the N phase. Combining the copolymer phase behaviors observed with the corresponding homopolymers TPP(n = 7) and TPP(m = 12), a phase diagram describing transition temperatures with respect to the composition can be constructed.

Corona poling of liquid crystalline polymers with nitroazobenzene side chains

The orientational behavior of liquid crystalline polymers with para-nitro azobenzene as side chains under electric field was studied by UV-visible spectroscopy. The results showed that lambda(max) of the poled polymer films was around 394nm, compared to that of the unpoled films, the absorption decreased due to poling. The orientational parameters increased linearly with the increase of the electric field. The temporal stability of the poled polymer film is good at room temperature. This kind of materials showed promise application as nonlinear optical component in photorefractive polymers.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 6. Structure changes from smectic to columnar phases in a series of copolyethers containing odd and even numbers of methylene units in equal molar composition

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

Synthesis and characterization of novel crosslinkable side-chain liquid crystalline polyesters

Crosslinkable side-chain liquid crystalline polyesters PCn from N-[n-(4-(4-nitrophenylazo)phenyloxy)alkyl]diethanolamine (Cn, n = 3, 5, 6, 10) as mesogenic monomers and maleic anhydride were synthesized and characterized. The thermal properties of PCn's were studied by means of DSC, polarized optical microscopy (POM) and wide angle X-ray diffraction (WAXD), and the results showed that all the polymers studied exhibit enantiotropic liquid crystallinity. In the molar mass independent region, the relatively high content of cis -CH=CH- groups in the polymer backbone of PC3 causes an increase of the melting temperature (T-m) and a decrease of T-g and isotropisation temperature (T-i). The crosslinking of PCn in the radical polymerization with styrene was confirmed by FTIR spectroscopy. The absorption band at 1300 cm(-1) attributed to the in-plane C-H-bending vibration of trans -CH=CH- in the polymer backbone disappeared after crosslinking, indicating that the trans -CH=CH- functions are consumed in the crosslinking polymerization of styrene.

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

Two closely series of poly(ester imide)s had been synthesized by solution polycondensation of p-phenylenebis(trimellitate) dianhydride with aliphatic diamines. The differential scanning calorimetry (DSC) traces of the most poly(ester imide)s exhibited two endotherms representing the solid state to anisotropic phase transition (T-m1) and the anisotropic to isotropic melt transition (T-m2), respectively. Observation under polarizing microscope and wide-angle X-ray diffraction (WAXD) measurements suggested that the anisotropic phase formed above the melting paints (T-m1) had a smectic character. The thermogravimetric analyses (TGA) revealed that the thermal stabilities of the poly(ester imide)s were up to 350 degrees C. (C) 1999 John Wiley & Sons, Inc.

Synthesis and Characterization of Side-Chain Liquid Crystalline (M6MPP/M6NPAP) Copolymers with NLO Properties

A series of novel thermotropic side-chain liquid crystalline polymer based on polymethacrylate backbone containing electron-accepting 4-(4'-nitrophenylazo)phenoxy as nonlinear optical active group and electron-donating 4(4'-methoxyphenyl) phenoxy group as mesogen attached covalently to the backbone through the flexible spacer was prepared and characterized, respectively. The results from differential scanning calorimetry showed that these series of copolymers were enantiotropic liquid crystal with single mesophase. The melting points and the relative enthalpy change of the copolymers depressed with increasing the molar percent of 4'-nitroazobenzene monomer units over 0 similar to 50mol%, but the enthalpies change of the transition from mesophase to isotropic state increased for the copolymers containing 0 similar to 50mol% 4'-nitroambenzene units. The texture observed under polarized optical microscope identified that the copolymers containing 24molar% or more than 24mol% 4-nitroambenzene monomer units could form smectic mesophase with the focal-conic texture. The results detected by WAXD were in good agreement with the results observed by POM.

The rheological and extrusion behaviour of blends based on phenolphthalein poly(ether-ether-sulfone) and thermotropic liquid crystalline polymer

A novel engineering thermoplastic, phenolphthalein poly (ether-ether-sulfone) (PES-C) was blended with a commercial thermotropic liquid crystalline polymer(TLCP), Vectra A950, up to 30 weight percent of TLCP. A rheometrics dynamic spectrometer (RDS-I) and a CEAST capillary rheometer, a rheoscope 1000 were employed to investigate the melt rheology and extrusion behaviour at both the low and high shearing rates. The morphologies of the blends under different shearing were observed with a scanning electron microscope(SEM) and correlated to the observed rheology. The principal normal stress differences measured with cone-and-plate geometry give a temperature-independent correlation for both blend and PES-C when they are plotted against shear stress. But the extrudate swell of the blends showed a strong temperature dependence at each shear stress. The concentration dependence of extrudate swell shows a contrary behaviour to that of the inorganic filled system. A reasonable hypothesis based on the relaxation and disorientation of TLCP during flowing in the capillary and exiting was given to explain it. The melt fracture was checked after extrusion from capillary and was discussed.