SYNTHESIS AND CHARACTERIZATION OF TRIAZOLE CONTAINING LIQUID CRYSTALLINE POLYMERS THROUGH 1,3-DIPOLAR CYCLOADDITION POLYMERIZATION

Liquid crystalline polymers containing 1,2,3-triazole units as linking groups have been synthesized from the monomers containing triad ester diazide and flexible dialkyne ester by 1,3-cycloaddition reaction and were characterized. Click reaction of azide and alkyne functionals catalyzed by Cu(I) yielded target polyesters with 1,2,3-triazole groups.The structure of the polymer was confirmed by spectral techniques.GPC analysis reveals that the polymers have moderate molecular weight with narrow distribution.H...

STABILITY OF EQUILIBRIA OF NEMATIC LIQUID CRYSTALLINE POLYMERS

We provide an analytical study on the stability of equilibria of rigid rodlike nematic liquid crystalline polymers （LCPs） governed by the Smoluchowski equation with the Maier-Saupe intermolecular potential. We simplify the expression of the free energy of an orientational distribution function of rodlike LCP molecules by properly selecting a coordinate system and then investigate its stability with respect to perturbations of orientational probability density. By computing the Hessian matrix explicitly, we are able to prove the hysteresis phenomenon of nematic LCPs： when the normalized polymer concentration b is below a critical value b＊ （6.T314863965）, the only equilibrium state is isotropic and it is stable; when b＊ 〈 b 〈 15/2, two anisotropic （prolate） equilibrium states occur together with a stable isotropic equilibrium state. Here the more aligned prolate state is stable whereas the less aligned prolate state is unstable. When b 〉 15/2, there are three equilibrium states： a stable prolate state, an unstable isotropie state and an unstable oblate state.

New conception in continuum theory of constitutive equation for anisotropic crystalline polymer liquids

A new continuum theory of the constitutive equation of co-rotational derivative type is developed for anisotropic viscoelastic fluid—liquid crystalline (LC) polymers. A new concept of simple anisotropic fluid is introduced. On the basis of principles of anisotropic simple fluid, stress behaviour is described by velocity gradient tensor and spin tensor instead of the velocity gradient tensor in the classic Leslie—Ericksen continuum theory. Analyzing rheological nature of the fluid and using tensor analysis a general form of the constitutive equ- ation of co-rotational type is established for the fluid. A special term of high order in the equation is introduced by author to describe the sp- ecial change of the normal stress differences which is considered as a result of director tumbling by Larson et al. Analyzing the experimental results by Larson et al., a principle of Non- oscillatory normal stress is introduced which leads to simplification of the problem with relaxation times. The special behaviour of non- symmetry of the shear stress is predicted by using the present model for LC polymer liquids. Two shear stresses in shear flow of LC polymer liquids may lead to vortex and rotation flow, i.e. director tumbling in the flow. The first and second normal stress differences are calculated by the model special behaviour of which is in agree- ment with experiments. In the research, the com- putational symbolic manipulation such as computer software Maple is used. For the anisotropic viscoelastic fluid the constitutive equation theory is of important fundamental significance.

SYNTHESIS AND PROPERTIES OF NEW MESOGEN-JACKETED LIQUID CRYSTALLINE POLYMERS

Some new mesogen-jacketed liquid crystalline polymers (MJLCP) with polymer backbones, spacers, and mesogenic units of different structures were synthesized by radical polymerization. The mesomorphic behavior of these polymers was examined using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Their liquid crystallinity is influenced by the variation of polymer backbone, spacer, mesogenic unit and its terminal groups. The results show that 1) a more flexible polymer main-chain is more favorable to the formation of a liquid crystal phase, while 2) a flexible spacer will decrease the 'Jacket Effect' and the liquid crystallinity and 3) a subtle modification of the terminal groups on the mesogenic unit may also have a significant influence on properties of the polymers.

WHOLLY-AROMATIC THERMOTROPIC LIQUID CRYSTALLINE POLYMER AND ITS BLOCK COPOLYMER

A wholly-aromatic thermotropic liquid crystalline polymer (WATLCP) composed of p-hydroxybenzoic acid (HBA), 4,4'-dihydroxy bisphenyl (BP), terephthalic acid (TPA), m-phthalic acid (MPA) was synthesized. It was symbolized by BP-LCP. Using a similar method, a new copolymer BP-PSF was prepared. BP-PSF has a semi-flexible chain polysulfone and a rigid-rod chain like BP-LCP. By FT-IR, polarizing microscope and DSC technique, the structures and properties of BP-LCP and BP-PSF were studied.

TRANSITIONS AND MODRPHOLOGY OF MAIN-CHAIN LIQUID CRYSTALLINE POLYMERS WITH X-SHAPED MESOGENS

The transitions and morphology of a series of main-chain liquid crystalline polymer with X-shaped mesogens were studied by means of DSC,SALS and polarizing microscopy techniques. Aneven-odd effect was observed for samples with different size of the substituents on the mesogenends. The isotropization process was similar to that of main-chain polymers with rod-likemesogens. No crystallization was detected for specimens cooling down from their isotropic meltstate. However two of the samples may crystallize in cooling process directly from the liquidcrystalline state.

EFFECT OF DRAWING ON MORPHOLOGY,STRUCTURE AND MECHANICAL PROPERTIES OF BLENDS OF A LIQUID CRYSTALLINE POLYMER AND MODIFIED POLY(PHENYLENE OXIDE)

Polymer strands with various draw ratios of a thermotropic liquid crystalline polymer (LCP) and modified poly(phenylene oxide) were prepared by drawing the melts leaving a slit die in open air. The morphology, structure and mechanical properties of the resulting strands were studied as a function of LCP content and draw ratio. It was found that the thermal and mechanical properties of the matrix phase did not change dramatically with the amount of LCP and draw ratio, but the orientation of LCP phase could be increased with draw ratio. The mechanical properties of the strands could be improved by moderately drawing the melts. Wide angle X-ray diffraction suggested that the improvement in tensile strength of the strands was due to the resultant fibrillation of LCP phase and enhanced molecular orientation. Morphological observation indicated that excessive drawing of the strands could lead to the break down of the microfibrils of LCP and thus resulted in the decrease of mechanical strength.

MORPHOLOGICAL AND KINETIC STUDIES OF PHASE TRANSITIONS OF A SIDE-CHAIN LIQUID CRYSTALLINE POLYMER

The morphological changes of a side-chain liquid-crystalline polymethacrylate during isotropization and liquid-crystallization transitions were studied by means of polarizing microscopy. These transitions were found to be composed of the initiation of a new phase at local places of the old phase matrix and the growth of the new phase: domains. The kinetics of the liquid-crystallization of the polymer from an isotropic melt to a smectic mesophase was also investigated. The isothermal process of the transition can be described by the Avrami equation. The values of the Avrami exponent were found to be around 2.6. which is lower than the value usually obtained for crystallization transition of polymers, but larger than that reported for liquid-crystallization transition of main-chain polymers. These results may indicate the difference in growth geometry of new phase during transition between crystallization and liquid-crystallization in general and between liquid-crystallization of main-chain and side-chain polymers. It was found that the liquid-crystallization of the used side-chain polymethacrylate may occur at small undercoolings with high transformation rate similar to that of main-chain polymers and small-molecule liquid crystals, while the crystallization of polymers can only proceed at large undercoolings. These phenomena can be explained by the idea that the surface free energy of nucleus during liquid-crystallization transition is less than that for crystallization, and evidence was obtained from analysis of the temperature dependence of the transformation rate.

Synthesis of Liquid Crystalline Polymers with Side Chains

The present paper covers the synthesis and characterization of several intermediate products, monomer, and polymers. 3-{ 2-[ 4-( 4-Nitrophenylazo ) phenoxy] ethyloxycarbonyl} propanoyloxy (2-hydroxy) propyl acrylate (4) was prepared by the ring-opening reaction of glycidyl acrylate with the monoester of succinic acid (3). The polymers (5) with different molecular weights were prepared by the free-radical polymerization. The polymers (5) had liquid crystalline behavior without decomposition as revealed by DSC, optical microscope.

LAMELLAR STRUCTURE OF THERMOTROPIC LIQUID CRYSTALLINE POLYMERS

The lamellar structure of a thermotropic aromatic polyester with flexible spacer has beenstudied by using transmission electron microscopy. It was found that the lamellar structure couldbe observed in the crystalline samples of this semirigid polymer crystallized from different states.The thickness of lamellae is around 10 nm, which is similar to that of the conventional polymersof flexible chain molecules. The molecular chains in the lamellae are oriented in the thicknessdirection as determined by electron diffraction. The possibility of molecular chains folding in the lamellae has been discussed.

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 Ⅱ) 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.

A NEW STRATEGY FOR THE DESIGN OF LIQUID CRYSTALLINE POLYMERS WITH FLEXIBLE AND APOLAR BUILDING BLOCKS

The synthesis and characterization of a new series of liquid crystalline polymers, poly(dicycloalkylvinylterephthalate)s, are reported. The basic building blocks of these polymers are not mesogenic by themselves. However,very stable mesophases can be generated by self-assembly of the polymer molecules. This approach suggests a novel designstrategy of liquid crystalline polymers with flexible and apolar building blocks.

MORPHOLOGICAL STUDIES OF A THERMOTROPIC SIDE-CHAIN LIQUID CRYSTALLINE POLYMER DURING MESOPHASE TRANSITIONS

The morphological features of a side-chain liquid crystalline polymer during the mesophase transitions were investigated by using the DSC technique. The polymer used was polyacrylate with mesogens of three benzene rings attached to the main chain through a flexible spacer. A special two-phase texture was observed in the transition temperature range. Similar to main-chain liquid crystalline polymers the transition process of the side-chain liquid crystalline polymer was composed of an initiation of the new phase at local places of the old phase matrix and a growth process of the new phase domains.

MELT BLENDS OF POLY (BUTYLEN TEREPHTHALATE) AND A THERMOTROPIC LIQUID CRYSTALLINE POLYMER

With the help of differential scanning calorimetry, cone-plate and capillary rheometry andscanning electron microscopy, a research has been conducted on rheological behavior,crystallization and morphology of poly (butylene terephthalate) (PBT) blends containing athermotropic LCP. The blend has zero entrance pressure loss, although the LCP has rather largeone. The viscosity curve of the blend lies between those of the LCP and PBT. The crystallizationof PBT is not affected by the presence of the LCP together with no indication oftransesterification between the two ingredients. LCP spheres and ellipsoids with the size of 0. 5--1. 5 μm disperse in PBT matrix uniformly, which is related to the viscosity ratio of the two components.

STUDY ON INTERMITTENT SHEAR FLOW AND RELAXATION BEHAVIOR OF THERMOTROPIC LIQUID CRYSTALLINE POLYMER

Intermittent shear flow including start-up flow and small oscillatory amplitude time sweep or stress relaxation aftercessation of shear flow was used to study the rheological behavior and internal structure of thermotropic liquid crystallinepolymer(TLCP).There are two kinds of intermittent shear flow:all start-up flows are in the same direction(intermittent flowforward:IFF)and start-up flows change their directions alternately(intermittent flow reversal:IFR).The results show thatthe stress of start-up flow of IFF and IFR in the test process is not superposed,indicating different changes of internalstructure of thermotropic LCP(TLCP).Two main factors affect structure changes in the experimental time scale.One relatesto long-term texture relaxation process,the other is an interchain reaction that becomes important after 30 min.The twofactors raise the stress of IFF,but express complex effects for the stress of IFR.The latter factor becomes very important atlong time annealing process.The relaxation behavior was also studied by the application of wide range relaxation spectrumcalculated from the combined dynamic modulus,which gave three characteristic relaxation times(0.3,10 and 600 s)ascribable to the relaxations of less-phase orientation,domain orientation,and domain deformation,respectively.The resultalso shows that the domain coalescence(texture relaxation),a long relaxation time,is a much slow process and lasts beyond2400 s of the test time.

STUDIES ON THE AGGRESGATION BEHAVIOUR OF A SIDE－CHAIN LIQUID CRYSTALLINE POLYMER IN LANGMUIR－BLODGETT FILMS

be aggregation behavior of a side chain liquid crystaline polymer (PSLC) has been investigated by means of surface pressure-area isotherm, TEM and SEM observation X-ray diffraction, and UV-vis spectroscopy. Resulte obtained can be explained by molecular exciton model.

STUDY ON CHIRAL LIQUID CRYSTALLINE POLYMERS WITH BIPHENYLENE AND AZOBENZENE AS THE MESOGENS

Chiral liquid crystalline polymers containing biphenylene and azobenzene as the mesogensand S(-)-2-methyl-1-butanol as the chiral end group were synthesized and characterized by DSC,POM and X-ray diffraction. These polymers show crystalline or glassy liquid crystalline phase atroom temperature. Most polymers show smectic A or highly ordered smectic phases abovemelting temperature.

A new constitutive theory for extrusion-extensional flow of anisotropic liquid crystalline polymer fluid

A new continuum theory of the constitutive equation of co-rotational derivative type was developed by the author for anisotropic viscoelastic fluid-liquid crystalline (LC) polymers (S.F. Han, 2008, 2010) . This paper is a continuation of the recent publication [1] to study extrusion-extensional flow of the fluid. A new concept of simple anisotropic fluid is introduced. On the basis of anisotropic simple fluid, stress behavior is described by velocity gradient tensor F and spin tensor W instead of the velocity gradient tensor D in the classic Leslie?Ericksen continuum theory. A special form of the constitutive equation of the co-rotational type is established for the fluid. Using the special form of the constitutive equation in components a computational analytical theory of the extrusion-extensional flow is developed for the LC polymer liquids - anisotropic viscoelastic fluid. Application of the constitutive theory to the flow is successful in predicting bifurcation of elongational viscosity and contraction of extrudate for LC polymer liquids–anisotropic viscoelastic fluid. The contraction of extrudate of LC polymer liquids may be associated with the stored elastic energy conversion into that necessary for bifurcation of elongational viscosity in extrusion extensional flow of the fluid.

Modeling Directionality of Liquid Crystalline Polymers on Arbitrary Meshes

The orientation of crystals in liquid crystalline polymers (LCPs) during the processing method affects the properties of these materials. In this paper, the main components of modeling the directionality of LCPs, namely Franks elastic energy equation, evolution equation and translation of directors are studied. The complexity of flow channels in polymer processing requires a more robust method for modeling directionality that can be applied to varieties of meshes. A method for practically simulating the directionality of crystallines on a macroscopic scale is developed. This method can be applied to any combination and type of meshes. The results show successful modeling of the directionality for each component of the model. Here, a 2D case with structured and unstructured mesh is considered and the rheology is simulated using ANSYS? FLUENT?. C++ codes written for user defined functions (UDFs) are used to implement the directionality simulation.

Co-rotational Oldroyd Fluid B Model for Spinning Flow of Liquid Crystalline Polymer

The relationship between the extensional viscosity and material parameters was studied through the analytical formulas of stress and extensional viscosity. The differential equations were solved to obtain the relationship between extensional viscosity and strain rates. The results obtained qualitatively agree with the experimental results. The study makes it practicable to simulate the rheologic behaviors of spinning flow of liquid crystalline polymer using co-rotational Oldroyd fluid B model.