INFLUENCE OF BACKBONE RIGIDITY ON THE LIQUID CRYSTALLINITY OF MESOGEN-CONTAINING POLYACETYLENES

Two acetylene polymers containing cyanobiphenyl-based mesogens, poly{10-[((4'-cyano-4-biphenylyl)oxy)carbonyl]-1-decyne} (PA8CN), which has a relatively flexible polyalkyne backbone, and poly {[4-(((12-((4'-cyano-4-biphenylyl)oxy)dodecyl)oxy) carbonyl) phenyl]-acetylene} (PB12CN), which has a fairly rigid poly(phenylacetylene) backbone, were synthesized using respectively WCl6 and [Rh(nbd)Cl](2) as the catalysts. PA8CN exhibits enantiotropic interdigitated smectic A phase (S-Ad) over a temperature range as wide as ca. 100 degrees C, whereas PB12CN is non-mesomorphic, demonstrating that the backbone rigidity plays an important role in determining the liquid crystallinity of the polyacetylenes.

STUDY ON LIQUID CRYSTALLINITY OF POLY(N-VINYLCARBAZOLE)

The liquid crystallinity of poly(N-vinylcarbazole) was studied by using powder X-ray diffraction, polarized opticalmicroscopy, and differential scanning calorimetry. The results show that the lower molecular weight fractions of this polymerdo not form a liquid crystalline phase, while the samples of sufficiently high molecular weight do form a mesophase attemperatures above the glass transition. The lowest value of the degree of polymerization for PVK to form a stable liquidcrystalline phase was found to be in the range of 150 to 200, significantly higher than the value of 50 for most conventionalside chain liquid crystaline polymers.

Helix-sense-selective radical polymerization of bulky styrenic monomers: chiral induction and liquid crystallinity

Eight chiral vinylterphenyl monomers, （＋）-2,5-bis{4＇-[（S）-1＂-methylpropyloxy]phenyl}styrene （Ia）, （＋）-2,5-bis{4＇-[（S）-2＂- methylbutyloxy]phenyl}styrene （Ib）, （＋）-2,5-bis{4＇-[（S）-3＂-methylpentyloxy]phenyl}styrene （Ic）, （＋）-2,5-bis{4＇-[（S）-4＂- methylhexyloxy]phenyl}styrene （Id）, （-）-2,5-bis{4＇-[（R）-1＂-methylpropyloxy]phenyl}styrene （le）, （＋）-2-/4＇-[（S）-l＂-methyl- propyloxy]phenyl}-5-{4＇-[（R）-1＂-methylpropyloxy]phenyl}styrene （Ⅱa）, （-）-2-{4＇-[（R）-1＂-methylpropyloxy]phenyl}-5-{4＇- [（S）- 1 ＂-methylpropyloxy]phenyl } styrene （lib）, and （＋）-2- { 4＇-[（S）-2＂-methylbutyloxy]phenyl }-5- { 4＇-[（S）- 1＂-methylpropyl- oxy]phenyl}styrene （Ⅲ）, were synthesized and radically polymerized. These molecules were designed to further understand long-range chirality transfer in radical polymerization and to possibly tune the chiroptical properties of the polymers by varying the spatial configuration, position, and various combination of the stereogenic centers at the ends ofp-terphenyl pendants. The resultant polymers adopted helical conformations with a predominant screw sense. When the stereogenic centers ran away from the terphenyl group as in Ⅰb-d, the corresponding polymers changed the direction of optical rotation in an alternative way and showed no obvious stereomutation upon annealing in tetrahydrofuran. The two stereogenic centers of Ⅱa, Ⅱb, and Ⅲ acted concertedly in chiral induction, whereas those of la and Ie played a counteractive role. The five polymers derived from Ⅰa, Ⅰe, Ⅱa, Ⅱb, and Ⅲ underwent stereomutation when annealed in tetrahydrofuran. The polymers PIa-e had good thermal stability and high glass transition temperatures （Tgs）. They generated liquid crystalline phases at above Tgs that could be kept upon cooling, with the exception of Pie. This result was consistent with the extended helical structures.

Synthesis and Phase Behavior of Poly(1-alkyne) with Liquid Crystalline-induced Luminescence Enhancement

Poly（1-alkyne） with octoxy spacer —{[HC=C（CH2）8O—terphenyl—CN]}n—（PA8CN） and terphenyl liquid crystalline pendant was synthesized,and the effects of structure on the optical properties,especially the liquid crystallinity behavior of the polymer and monomer were investigated.The monomer was prepared in high yields（92.30%） by coupling and etherification reactions and successfully polymerized in the presence of Rh catalyst and Et3N cocatalyst in high yields with trans-rich（86.27%） stereoregular structure.Compared to the monomer showing mixed monolayer structure,its corresponding polymer PA8CN formed homogeneous monolayer arrangement.Upon photoexcitation,strong blue emission peak of PA8CN appeared at 413 nm[fluorescence quantum yield,ΦF = 68% when excited at 330 nm in tetrahydrofuran（THF） solution].Compared with its solid film photoexcitated at 330 nm at room temperature,the UV light-emitting band of PA8CN solid film from its liquid crystalline with liquid nitrogen quenched rapidly at 236 ℃ was red-shift 10 nm with higher intensity,which may be ascribed to the fact that the effectual conjugation and the order degree of the molecule in the liquid crystalline state of the polymer were enhanced,the energy loss caused by the thermal vibration was decreased,thus resulting in the observed hyperchromic effect.

A three-dimensional co-continuous network structure polymer electrolyte with efficient ion transport channels enabling ultralong-life all solid-state lithium metal batteries

Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility with electrodes.Herein,a novel all-solid polymer electrolyte(PPLCE)was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol)dimethacrylate(PEGDMA)acts as a structural frame,combined with poly(ethylene glycol)diglycidyl ether short chain interspersed serving as mobile ion transport entities.The preparaed PPLCEs exhibit excellent mechanical property and out-standing electrochemical performances,which is attributed to their unique three-dimensional cocontinuous structure,characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase,resulting in a distinctive nanostructure with short-range order and long-range disorder.Remarkably,the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs,which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte.When used in a lithiumion symmetrical battery configuration,the 6 wt%-PPLCE exhibites super stability,sustaining operation for over 2000 h at 30 C,with minimal and consistent overpotential of 50 mV.The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g^(-1)at current densities of 0.2 and 1 C,respectively.Even after more than 300 cycles at a current density of 0.2 C,it retaines an impressive 73.5%capacity.Moreover,it displayes stable cycling for over 180 cycles at a high current density of 0.5C.The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.

SYNTHESIS AND CHARAOTERIZATION OF NOVEL THERMOTROPIO LIQUID ORYSTALLINE POLYESTERS BEARING NONLINEAR OPTICAL AZOBENZENE SIDE GROUP

A series of novel thermotropic liquid crystalline polyesters bearing nonlinear optical azobenzene side group were synthesized by high temperature solution polycondensation and their structures,thermal stability, phase transition behavior and crystallinity were characterized by IR,elemental analysis, TG-DTA, polarizing optical microscope (POM) equipped with a hot stage and X-ray diffraction techniques. The results demonstrate that all the synthesized polyesters exhibit nematic liquid crystalline phases and show relatively high glass transition temperatures and good thermal stability.

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.

Compatibilization of PBT/PP Blends by Adding Side-chain Liquid Crystalline Ionomer with Quaternary Pyridinium Groups

A side-chain liquid crystalline ionomer（SLCI） was synthesized by grafting copolymerization of 4-（4-ethoxybenzoyloxy）-4＇-allyloxybiphenyl and N-allyl-pyridium bromide on polymethylhydrosiloxane. The SLCI was blended with polypropylene（PP） and polybutylene terephthalate（PBT） by melt mixing. The thermal behavior, liquid crystalline properties, morphological structure, and mechanical properties of the blends were investigated by differential scanning calorimetry（DSC）, polarizing optical microscopy（POM）, scanning electron microscopy（SEM）, and tensile measurement. When a proper amount of SLCI was added, fine configurations were formed in the PBT/PP/SLCI blend system, and the mechanical properties were improved due to improved adhesion at the interface. When excess SLCI was added, an inhomogeneous structure resulted, which caused the mechanical properties to deteriorate.

Synthesis and characterization of H-type amphiphilic liquid crystalline block copolymers by ATRP

H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene oxide） （PEG） and 2,2-dichloroacetyl chloride were utilized to initiate the polymerization of 6-[4-（4-ethoxyphenylazo）phenoxy]hexyl rnethacrylate （M6C）. The resulting macroinitiators and block copolymers were characterized by ^1H NMR, gel permeation chromatography （GPC）. Polarizing optical microscopy （POM） and differential scanning calorimetry （DSC） preliminarily revealed the liquid crystalline property of these block copolymers. This series of liquid crystalline block copolymers are promising in some areas, such as optical data storage, optical switch, and molecular devices.

Effect of spacer length on the liquid crystalline property of azobenzene-containing ABA-type triblock copolymers via ATRP

The effect of flexible spacer length on the liquid crystalline property of ABA-type triblock copolymers containing azobenzene groups was investigated. For the study, the monomers, n-[4-(4-ethoxyphenylazo)phenoxy]alkyl methacrylates with varying methylene groups (n = 0, 2, 6) were used to synthesize a series of azobenzene-containing amphiphilic triblock copolymers PAnC–PEG–PAnC by atom transfer radical polymerization (ATRP). Differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and one-dimensional X-ray diffraction (1D WAXD) have shown that the glass transition temperatures of these copolymers decreased with increasing n, PA0C–PEG–PA0C has no mesophase, while both PA2C–PEG–PA2C and PA6C–PEG–PA6C have a nematic mesophase. These differences derive from the length of spacer groups between the polymer backbone and side-chain LC monomers.

SIDE CHAIN LIQUID CRYSTALLINE POLYSILOXANES CONTAINING CROWN ETHER AND BENZYL ETHER MOIETIES

Two kinds of side chain liquid crystalline polysiloxanes containing crown ether and benzyl ether were synthesized and characterized by optical polarization microscopy. Both the monomeric liquid crystals and polymeric liquid crystals show smectic phases.

Synthesis,liquid crystalline and luminescent properties of trimeric phenylenevinylene with end-groups of(R)-(+)-2-methylbutyric acid ester

The trimeric phenylenevinylene with the symmetrical chiral end-groups （ChTPV） was synthesized. The liquid crystalline and luminescent properties of the ChTPV have been studied by differential scanning calorimetry （DSC）, polarized optical microscopy （POM）, absorption and photoluminescence spectra. The results indicated that the ChTPV exhibits mesophase over a wide temperature range and a typical optical texture of smectic phase. In contrast with the spectra of the solution, that of the film showed blue-shift in maximal absorption and red-shift in maximal emission due to H-type aggregation with parallel alignment of the TPV transition dipole moment.

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.

Modification of Interfacial Interaction of PBT/PP Blends by Adding Main-chain Liquid Crystalline Ionomer with Sulfonic Group

A main-chain liquid crystalline ionomer（MLCI） containing sulfonic group was synthesized by an interfacial condensation reaction.The MLCI was blended with polybutylene terephthalate（PBT） and polypropylene（PP）.MLCI interacted with both the dispersed（PP） phase and the matrix（PBT） phase to modify the interfacial interaction of PBT and PP.Differential scanning calorimetry（DSC）,scanning electron microscopy（SEM） and FTIR imaging system analysis demonstrated the significance of interfacial interaction in the polymer blends.MLCI brought about good adhesion at the interfacial,which reduced the disperse phase size and enabled a fine PP phase at matrix.The mechanical properties of the ternary blends were improved when a proper amount of MLCI was added.This was attributed to enhanced adhesion at the interface,which invoked better mechanical properties in the blends.

Synthesis and Characterization of New UV-curable Liquid CrystallineDiacrylates

A series of UV-curable liquid crystalline diacrylates were synthesized by using 4, 4'-(terephthaloyldioxy) dibenzoic acid as a mesogen unit.

CHOLESTERIC LIQUID CRYSTALLINE CHARACTER ON THE SURFACE OF CHITOSAN/POLYACRYLIC ACID COMPOSITES

The cholesteric liquid crystalline structure in chitosan/polyacrylic acid composite films was studied by surface techniques. A periodical lamellar-like structure was observed in the permanganic acid etched film surface by both scanning electron microscopy (SEM) and atomic force microscopy (AFM), instead of the thumb-print texture which can be detected with polarized optical microscopy. It is suggested that the periodical lamellar-like structure is induced by the etching selectivity between cholesteric layers due to different molecular arrangement on the film surface. Four kinds of perpendicular disclinations, i.e. chi --> tau (-) + lambda (+), chi --> lambda (-) + tau (+), chi --> tau (-) + tau (+) and chi --> lambda (-) + lambda (+) were found in the composite films from SEM observations. The smallest periodicity of lamellar-like structure (equals to half pitch) is 20 similar to 40 nm measured with AFM.

SYNTHESES AND CHARACTERIZATION OF A NEW TYPE OF LIQUID CRYSTALLINE POLYESTERS

A new type of liquid crystalline polyesters with resorcin as one part of the mesogenic unitconnected together by polymethylene, or phenylene group, and lateral groups consisting of arigid azobenzene as another part of the mesogenic unit were synthesized by interfacialpolymerization of diacyl chlorides in 1, 2-dichloroethane and 2, 4-dihydroxy-4'-nitroazobenzen inaqueous alkaline solution. The polyester structures were confirmed by proton NMR and IRspectra. Their phase transition behavior and texture were studied by polarizing microscopy andDSC.

STUDY ON THE BLENDS OF NYLON 66 AND LIQUID CRYSTALLINE POLYESTERS

Blends of polyamide (Nylon 66) with two different kinds of liquid crystalline polyesters were studied in all the composition range. Homogeneous samples were obtained by coprccipitation from 2 wt%. solution of blends. The thermal properties, crystallinity and morphology of these blends were studied by using DSC, polarizing microscopy, and scanning electron microscopy. The phase transition and morphology of the blends are markedly-influenced by the composition of liquid crystalline polyesters. The mechanical behaviour of PHB/HNA-Nylon 66 blend was improved. although polyamidc (Nylon 66)with the liquid crystalline polyesters were incompatible, but a rather strong interaction between the polymers did exist.

MECHANICAL PERTURBATION INDUCED MOLECULAR ALIGNMENTS IN A SIDE-CHAIN LIQUID CRYSTALLINE POLYACETYLENE, POLY{10-[4-(4'-METHOXYPHENOXY-CARBOML)PHENOXYCARBONYL]-1-DECYNE}

A new liquid crystalline polyacetylene containing a phenyl benzoate mesogen (5) is synthesized,whose mesomorphic properties are found to be easily 'tunab1e' by simple mechanical perturbation. Thepolymerization of 10- [ 4 - (4' -methoxyphenoxycarbonyl )phenoxycarbonyl] - 1 -decyne (4 ) in itiated by theWCl_6-Ph_4Sn/dioxane complex yields polymer 5 with a M_w of 28400. The molecular structure of 5 ischaracterized by NMR, IR, and UV spectroscopy and its liquid crystalline behavior is investigated by DSC,POM, and XRD analysis. Upon mechanical perturbation, 5 exhibits unusual agitation-induced high-strengthdisclinations, shear-induced inversion walls, and solidification-induced banded textures. Such phenomenahave been observed in the main-chain liquid crystalline polymers with rigid backbones, but have seldom beenreported for the side-chain liquid crystalline polymers with flexible backbones, suggesting that the rigidpolyacetylene backbone of 5 plays a constructive role in inducing the novel molecular alignments.