Fast switching ferroelectric liquid crystal side chain polymer

Two products were isolated at a result of esterification of acrylic acid with 4-[4-(n-hydroxyundecanyloxy)phenyl] benzoic acid (5) One is 4-[4-(n-acryloloxy-undecanyloxy)phenyl] benzoic acid (6), and the other is 4-{4-[n-(3-acryloloxy-propionyloxy)undecanyloxy]phenyl}benzoic acid (7) which containts two molecules of acrylic acid. Compound7 is obtained unexpectedly and still unknown in the literature. Its identification is confirmed by the isolation and characterization of the monomer9. The mesogenic monomers8 and9 which were synthesized from 4-hydroxyphenyl 2(S)-[2(S)-methylbutoxylpropionate (4) and the corresponding acrylates6 and7 exhibit the enentiotropic Sc* and S_A phases. The Sc^* phase temperature range is up to 31 °C. The spontaneous polarization and response time for the monomers8 and9 is 97 and 16 nC/cm² as well as 90 and 64 µs respectively. It us the liquid crystal side chain polymer11, not10, which is switchable in the presence of an electric field. The spontaneous polarization of 36 nC/cm² and the response time of 3.1 ms is obtain from the new polyacrylate.     

Synthesis and characterization of high molecular weight side chain liquid crystalline/photoactive polymers

Various liquid crystalline and photoactive azobenzene monomers were synthesized and attached to copoly(methyl methacrylate‐glycidyl methacrylate) [copoly (MMA‐GMA)] to get high molecular weight side chain liquid crystalline (LC)/photoactive copolymers. Further, spacers are generated in situ and reactive groups are obtained after the modification. All monomers and polymers were thoroughly characterized by FTIR, ¹H and ¹³C NMR, UV‐VIS spectrophotometry, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy. All side chain LC polymers showed higher thermal stability than that of copoly(MMA‐GMA). Three LC and one azo monomer exhibited characteristic nematic mesophase where as one LC monomer has shown nematic and sanded smectic‐A texture. The rate of trans‐cis isomerization of polymer was lower than that of the monomer and both monomers and polymers showed slow back isomerization. Present approach offers convenient way to synthesize high/desired molecular weight photoactive LC polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Molecular orientation in quenched channel flow of a flow aligning main chain thermotropic liquid crystalline polymer

We report measurements of molecular orientation in solid specimens of a main-chain thermotropic liquid crystalline polymer (LCP) that were quenched from mixed shear-extensional channel flows. The polymer under investigation is a random copolyether with mesogens separated by flexible hydrocarbon spacers. This polymer is known to exhibit ‘flow aligning’ dynamics under slow shear flow. Experiments were designed to preserve the molecular orientation state, representative of steady, isothermal channel flow in the solid samples, so that comparisons could be made against in situ channel flow measurements on other main chain thermotropes without flexible spacers, including a commercial fully aromatic copolyster. In the flow aligning material, little change in orientation was found in slit-contraction flows, and only modest drops in orientation were found in slit-expansion flow. This contrasts strongly with data on commercial LCPs, suggesting that these materials may be of the ‘tumbling’ type.     

Phase behaviour and bistable effect of a mixture comprising a dye side chain liquid crystalline polymer and a low molecular weight liquid crystal

Phase behaviour and bistable effect of dye side chain liquid crystalline polymer (dye LCP)/low molecular weight liquid crystal (LC) mixtures have been investigated. The smectic dye LCP was observed to be miscible with the nematic LC over wide ranges of concentration and temperature. The electro-optical effects of the dye LCP/LC mixtures could be classified into the turbid and the transparent states upon a respective application of electric fields at low and high frequencies. Both transparent and turbid states of the mixture could be maintained stable, despite an electric field having been turned off.     

Mesogen-jacketed liquid crystalline polymers substituted with oligo(oxyethylene) as peripheral chain

Mesogen-jacketed liquid crystalline polymer (MJLCP) is a typical rod-shaped macromolecule. Its unique molecular architecture allows one to tune the geometric parameters of the macromolecular rod. Moreover, the rod surface chemistry can be controlled by designing the peripheral groups of the lateral mesogens. In previous work in this system, short alkyl chains have been used and the resultant macromolecular rods therefore have a hydrophobic surface. In this paper, we report using oligo(oxyethylene) groups as the peripheral groups of the lateral mesogens. Poly{{2,5-bis[4-methoxyoligo(oxyethylene)phenyl]oxycarbonyl}styene} (PnEOPCS) with different oligo(oxyethylene) chain length has been synthesized. These oligo(oxyethylene) groups led to macromolecular rods with hydrophilic surface. Differential scanning calorimetry, polarized light microscopy, and one-/two-dimensional wide-angle X-ray diffraction experiments were carried out to study the phase structures and phase behaviors of this series of polymer. The existence of flexible polar groups lowered the glass transition temperatures of PnEOPCS. All polymers studied showed supramolecular columnar nematic or hexatic columnar nematic phase, which arose from the parallel alignment of the polymer supramolecular rods. The diameter of the cylindrical building block increased with increasing the length of the oligo(oxyethylene) groups. The macromolecular rod surface can be further tuned by complexation the oligo(oxyethylene) with lithium salts. Detailed study showed that this complexation also tremendously affected the liquid crystalline phase of the polymer.     

Photoinduced molecular reorientation in photoreactive liquid crystalline copolymers in a phase retarder application

Polymethacrylate copolymers, which have hexamethylene spacer groups terminated with 4-methoxyphenyl-4′-oxycinnamate (MPC) and 4-oxybenzoic acid (BA) in the side chain, were synthesized. Thin films underwent thermally enhanced photoinduced cooperative molecular reorientation using linearly polarized ultraviolet (LPUV) light and subsequent annealing. Moreover, low exposure energy (4-80 mJ cm⁻²) and annealing temperature (<140 °C) provided sufficient cooperative molecular reorientation of both side groups with a large reorientational order (S > 0.5). Tuning the copolymer composition adjusted the birefringence (?n) of homogeneously reoriented films between 0.10 and 0.22 at 517 nm. Finally, a phase retarder (?nd = 130 nm) using an oriented copolymer on a triacetylcellulose (TAC) film substrate, which exhibited a thermal stability up to 140 °C, was fabricated.     

Measurement of molecular orientation in thermotropic liquid crystalline polymers

Procedures for obtaining molecular orientational parameters from wide angle X-ray scattering patterns of samples of thermotropic liquid crystalline polymers are presented. The methods described are applied to an extrusion-aligned sample of a random copolyester of poly(ethylene terephthalate) (PET) and p-acetoxybenzoic acid. Values of the orientational parameters are obtained from both the interchain and intrachain maxima in the scattering pattern. The differences in the values so derived suggest some level of local rotational correlation     

Determination of the molecular orientation in the polymeric liquid crystalline systems by low frequency Raman spectroscopy

Anisotropic polymer composites with fixed, oriented liquid crystalline organisation prepared by in situ photopolymerisation of acrylic or methacrylic acids in several cellulose derivatives were investigated by low frequency Raman scattering. The results were interpreted basing on a model of non-continuous structure of polymer glasses. The Raman investigations have shown that the macromolecules of the non-mesogenic (acrylic) component are oriented in the anisotropic composites, and that the orientation of the polyacrylic chains is more pronounced in the composites with higher concentration of the liquid crystalline cellulose derivative. It was found, that the interactions between the components play a crucial role in the formation of the composites (template-like photopolymerisation) and they determine their supramolecular structure. The liquid crystalline cellulose derivatives able to form hydrogen bonds play a role of specific cross-linking agents, while the cellulose derivatives with aliphatic side chains work as plasticisers.     

Influence of alkylene spacer length on photoinduced molecular reorientation and LC alignment behavior in photo-cross-linkable liquid crystalline polymeric films with H-bonded cinnamic acid side groups

Photoinduced reorientation of liquid crystalline polymethacrylates comprised of various lengths of alkylene spacers terminated with 4-oxycinnamic acid in the side chain and low-molecular liquid crystal (LC) alignment on the resultant photoreacted films were investigated using linearly polarized UV light. As the length of the spacer increased, the photoinduced optical anisotropy (ΔA) of the thin films increased, and ΔA increased as the irradiating temperature increased. Exposing the polymeric films in the LC temperature range of the material generated an in-plane molecular reorientation because the small photoinduced ΔA was simultaneously amplified. The low-molecular LCs aligned homogeneously on the photoreacted polymeric films, but the LC alignment direction depended on the alkylene spacer length and the degree of the photoreaction.     

Ordering-induced micro-bands in thin films of a main-chain liquid crystalline chloro-poly(aryl ether ketone)

Micro-banded textures developed from thin films of a main-chain thermotropic liquid crystalline chloro-poly(aryl ether ketone) in the melt were investigated using transmission electron microscopy (TEM), selective area electron diffraction, and atomic force microscopy techniques. The micro-banded textures were formed in the copolymer thin films after annealing at temperatures between 320 and 330 °C, where a highly ordered smectic crystalline phase is formed without mechanical shearing. The micro-banded textures displayed a sinusoidal-like periodicity with a spacing of 150 nm and an amplitude of 2 nm. The long axis of the banded texture was parallel to the b-axis of an orthorhombic unit cell. In the convex regions, the molecular chains exhibited a homeotropic alignment, i.e. the chain direction was parallel to the film normal. In the concave regions, the molecular chains possessed a tilted alignment. In addition to the effects of annealing temperatures and times, the thickness of the film played a vital role in the formation of the banded texture. A possible formation mechanism of this banded texture was also suggested and discussed. It was suggested that the micro-bands were formed during cooling.     

Effects of molecular weight on liquid-crystalline behavior of a mesogen-jacketed liquid crystal polymer synthesized by atom transfer radical polymerization

The synthesis of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) with different molecular weight and low polydispersity was achieved by atom transfer radical polymerization in methoxybenzene solution using 1-bromoethylbenzene as an initiator and CuBr/sparteine complex as a catalyst. The concentration of the living centers throughout the polymerization was found to be constant. The liquid-crystalline behavior of the polymers with M_n ranging from 3800 to 17,400 g/mol was studied using DSC and POM. Only the polymers with M_n beyond 10,200 g/mol formed a liquid-crystalline phase, which was quite stable with a high clearing point (higher than the decomposition temperature of the polymer).     

Viscoelastic properties of ternary in situ elastomer composites based on fluorocarbon, acrylic elastomers and thermotropic liquid crystalline polymer blends

Dynamic mechanical analysis was performed to characterize the viscoelastic properties of binary and ternary blends of fluorocarbon elastomer (FKM), acrylic elastomer (ACM) and liquid crystalline polymer (LCP). The results showed that the storage and loss modulus of all the blends increased significantly with the weight percentage of the LCP. The glass transition temperature evaluated at the loss modulus peak, were in the range of −10-+5 °C for all the blends. The time temperature superposition principle was applied for the FKM/ACM and 20% LCP filled FKM/ACM blend in order to evaluate the changes in the viscoelastic properties of FKM/ACM blend by the addition of LCP. The Arrhenius and William-Landel-Ferry (WLF) equations were used to quantify the viscoelastic behaviour at the glass transition region. Both the blends exhibited a single relaxation, which is glass transition, observed as a peek in the loss modulus at 1 Hz. The glassy moduli of these two systems were found to be comparable, but the rubbery moduli of the LCP filled FKM/ACM was much higher than the LCP unfilled system. However, the viscoelastic behaviour of these two systems and their sensitivity to time temperature may be considered to be quite similar.     

Kinetics of the ordered phase growth at the phase transition from the isotropic to cholesteric state in a main chain liquid crystalline polymer

The optical microscope investigation of the isotropic- ordered phase transition in a main chain LC polymer and subsequent statistical treatment of the microscopic images allowed recognition of three regimes of the ordering: non-stationary regime which is characterized by increasing rate of the droplets growth; stationary regime; within it the ordered phase grows with a constant rate, and the coalescence regime for which the rate of the droplets growth deceases. Linear interpolation of the time dependence of the mean droplets diameter in log–log scales allowed conclude that within the stationary regime of the cholesteric phase growth, log <d> is a linear function of log t, whereas within the coalescence regime, <d> is proportional to t ^1/2 as expected from the theory of phase separation binary liquids. The time of beginning and duration of both growth regimes of the phase transition for the main chain LC polymer exceed those for low molecular weight LC compounds. This is caused by lower mobility of macromolecules in comparison with that for low molecular weight LC compounds.     

Dynamic interfacial properties between a flexible‐chain polymer and a thermotropic liquid crystalline polymer investigated by an ellipsoidal drop retraction method

In this study, the dynamic interfacial properties between an isotropic polymer and a thermotropic liquid crystalline polymer (TLCP) were investigated by measuring the time‐dependent interfacial tension between them. As a TLCP drop retracts in a flexible polymer matrix, the evolution of its shape is recorded by microscopy. By fitting the ellipsoidal model of Maffettone and Minale, the model of Marrucci and Santo, and large deformation ellipsoidal models by Jackson–Tucker and Yu–Bousmina, the interfacial tension could then be determined. It was found that the retraction of a TLCP ellipsoidal drop in a flexible polymer cannot be described by these models as accurately as in Newtonian systems. The apparent interfacial tension obtained from these models evolves with time; the evolution is ascribed to the slow relaxation of domain orientation within the TLCP drop. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94:1404–1410, 2004     

Preparation of polymer‐dispersed liquid crystal films containing a small amount of liquid crystalline polymer and their properties

Polymer‐dispersed liquid crystal (PDLC) films were synthesized by the copolymerization of liquid crystalline polymer (LCP) precursor, urethane acrylate (UA), and mesogenic monomer (AI) at different conditions. The morphology of polymer matrix changed with the weight ratio of polymer/liquid crystal (LC) ratio and curing temperature, resulting in a large change in the droplet size of LC domains in the PDLC film. The components used in the synthesis of polymer matrix, that is, the weight ratio of LCP, AI, and UA, also strongly influenced the morphology of PDLC films. A small amount of LCP was copolymerized with UA and AI in the preparation of polymer matrix to improve the electrooptical properties such as the viewing angle. Added LCP also affected the morphology and the properties of PDLC. The hydrophobicity of LCP caused changes in the droplet size of LC domain in PDLC films and the anchoring energy between matrix polymer and LC droplets. As the hydrophobicity of the matrix increases, the droplet size of LC domain also increases; on the contrary, anchoring energy decreased, leading to the decrease of driving voltage. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3178–3188, 2000     

Evolution of morphological and rheological properties along the extruder length for blends of a commercial liquid crystalline polymer and polypropylene

The main aim of this work is to study the morphological and rheological evolution during extrusion of blends of polypropylene and a commercial liquid crystalline polymer, Rodrun LC3000. This study was performed for blends with 10, 20 and 40 wt% LCP, processed at 220 and 240 °C. For this purpose, a special collecting device was used that allows the removal of samples at different locations along the extruder length. The results of the morphological study revealed that the mean diameter of the LCP structures decrease as they proceed along the extruder axis. The rheological properties were also studied ex situ both in the linear and in the non-linear regime. From the results obtained in oscillatory shear it was observed that the elastic modulus and the complex viscosity decreases from the beginning to the end of the extrusion process, reaching a minimum for the final extrudate. FT rheology was used to study the non-linear viscoelastic behavior and the results also show marked difference between samples collected at various stages of the process, the ratio I(3ω₁)/I(ω₁) decreasing along the extruder.     

Electro-rheological effect and dynamic rheological properties of a blend composed of two liquid crystalline materials with different molecular weight

Electro-rheological (ER) effect of a blend composed of two liquid crystalline materials with different molecular weights is described in this article. The results indicated that ER effect of the blend was observed at the temperature range where each neat sample did not show ER effect. Furthermore, both storage modulus (G′) and loss modulus (G″) decreased drastically at the temperature range for the blend in dynamic viscoelastic measurements. We show that steady ER effect could be obtained by using a blend made up of two liquid crystalline components, whereas remarkable increment in shear stress was not observed for each component under applied electric field.     

Synthesis and characterization of diblock copolymers based on crystallizable poly(ε-caprolactone) and mesogen-jacketed liquid crystalline polymer block

Diblock copolymers comprising crystallizable poly(ε-caprolactone) and poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) were synthesized by ring-opening polymerization of ε-caprolactone and subsequent atom transfer radical polymerization (ATRP) of MPCS. The molecular structure of the copolymers was confirmed by ¹H NMR spectroscopy and GPC. Kinetic study of ATRP showed that the polymerization proceeded in a controlled way up to high conversions. Three series of diblock copolymers were obtained with relatively narrow polydispersity indices (PDI≤1.11) and PCL blocks of 8000, 12,900, and 22,800 molecular weights, respectively. The existence of microphase separation was identified by differential scanning calorimetry (DSC) and directly observed through transmission electron microscopy (TEM). The melting behavior of PCL block was significantly affected by the length of PCL block and composition of PMPCS. The thermotropic liquid crystalline behavior was examined by polarized optical microscopy (POM) and DSC. The result showed that the diblock copolymer exhibited liquid crystalline behavior when the degree of polymerization (DP) of PMPCS block was not less than 44.     

Synthesis, characterization and mesomorphic behavior of liquid crystalline copolysiloxane polymers: III. With an oligo(ethylene oxide) unit and a cyano unit in the side chain

The syntheses and characterizations of copolymers (poly [(MS3BDBE3)-co-(MCN)]_x,y) (where x/y represents the molar ratio of the two structural units on the side chain) were accomplished in this study. Differential scanning calorimeter (DSC) was used to determine the transition temperatures, enthalpy changes and entropy changes of the mesophase phase. The layer spacings (d1) in the mesophases of the homo-and co-polysiloxanes were determined by an X-ray diffractometer equipped with a temperature-controlling Pt hot stage. From DSC thermal data and X-ray diffraction analysis, we found both mixed and double bilayer smectic C mesophases at lower MCN concentrations and a mixed and bilayer smectic A mesophases at higher MCN concentrations. The microstructures of the copolymers poly [(MS3BDBE3)-co-(MCN)]_x/y are different from those of the copolymers poly [(MS3BDBE1)-co-(MCN)]_x,y reported previously. Mesophase and layer spacing of the copolymer are dependent on the MCN concentration in the copolymer. Incorporation of MCN into the copolymer increases the entropy change, which is the result of a loss of positional order contributed by conformational or orientational disorder.