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.

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.

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.

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.

Thermo-and photo-driven soft actuators based on crosslinked liquid crystalline polymers

Crosslinked liquid crystalline polymers（CLCPs） are a type of promising material that possess both the order of liquid crystals and the properties of polymer networks.The anisotropic deformation of the CLCPs takes place when the mesogens experience order to disorder change in response to external stimuli; therefore,they can be utilized to fabricate smart actuators,which have potential applications in artificial muscles,micro-optomechanical systems,optics,and energyharvesting fields.In this review the recent development of thermo-and photo-driven soft actuators based on the CLCPs are summarized.

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.

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.

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.

Alkyl-thiophene-alkyl linkers to construct double-cable conjugated polymers for single-component organic solar cells

In this work,semirigid linkers of the alkyl-thiophene-alkyl structure are developed to construct double-cable polymers.Three alkyl units,propyl(C3H6),hexyl(C6H12),and dodecyl(C12H24),are applied as semirigid linkers,yielding three double-cable polymers:PBC6-T,PBC12-T,and PBC24-T,respectively.PBC12-T which uses C6H12-thiophene-C6H12 linkers is found to exhibit the best device efficiency of 5.56%,while PBC6-T and PBC24-T with shorter or longer linkers yield device efficiencies of only 2.65%and 1.09%in single-component organic solar cells(SCOSCs).Further studies reveal that PBC12-T exhibits higher crystallinity and improved charge transport,resulting in better efficiencies.Our work provides an approach to construct double-cable conjugated polymers with long alkyl linkers,and it shows the importance of the linker length for the photovoltaic performance of SCOSCs.

Multiple Effects Tailoring the Self-organization Behaviors of Triphenylene Side-chain Liquid Crystalline Polymers via Changing the Spacer Length

Long-alkyl tail triphenylene （TP） side-chain liquid crystalline polymers （SCLCPs） with different spacer length （P-m-TP, m = 2, 3, 4, 6, 8, which is the number of carbon atom in the flexible alkyl spacers） have been successfully synthesized via free radical polymerization. The differential scanning calorimetry （DSC）, polarized light microscopy （POM）, ultraviolet-visible spectroscopy （UV- Vis）, wide-angle X-ray diffraction （WAXD） and small-angle X-ray scattering （SAXS） measurements were performed to investigate the influence of multiple effects on the self-organization behaviors of P-m-TP, including steric effect, decoupling effect and π-π stacking effect. The experimental results revealed that P-m-TP （m = 2, 3, 4） formed the columnar phase which was developed by the TP moieties and the main chain as a whole, suggesting that the side-chains had strong steric effect even though the number of spacer length （m） exceeded 4. In addition, the clearing points （Tis） of the polymers were above 300 ℃. When m = 6 and 8, the polymers displayed hexagonal columnar phase and exhibited the low Tis （91 and 80 ℃ respectively）, originating from the self-assembly of triphenylene due to the decoupling effect and π-π stacking effect. This work offers a viable and inspiring pathway to control the phase transition temperature and phase structure ofTP SCLCPs via simply tailoring the spacer length and increasing the alkyl tail length of TP.

AIEgen containing side-chain liquid crystalline polymers: Photoluminecence or photothermal, which dominate?

Why many luminescent liquid crystalline polymers(LLCPs)containing aggregation-induced emission luminogen(AIEgen)show weak emission is a question still to be answered.Herein,a series of LLCPs(α-Pns,n=4,8,and 12)with polynorbornene as main chain and twoα-dicyanodistyrylbenzene(α-DCS)as side chain are successfully synthesized to solve this issue.Differential scanning calorimetry(DSC),polarized light microscopy(PLM),one-dimentional(1D),two-dimentional(2D)middle-angle and wide-angle X-ray scattering(MAXS and WAXS)results demonstrate that the polymers form smectic A(SmA)phase with the side chains interdigitated packed within the smectic layers.Meanwhile,the photophysical properties ofα-Pns were investigated by ultraviolet-visible(UV-vis)absorption,steady state and time-resolved spectroscopy,and photothermal effect.Results show that the polymers are AIE active,but emit weak emission.The emission peak ofα-Pns film red-shift from 473 to 531 nm,the quantum yield gradually increases from around 1.6%to 14.7%,and the photothermal conversion efficiency decreases from 39%to 19%with the alkyl tail length increased.The photothermal effect,but not photoluminescence,dominates the excited state relaxation.

Synthesis and Liquid Crystalline Behavior of Side Chain Liquid Crystalline Polymers Containing Triphenylene Discotic Mesogens with Different Length Flexible Spacers

A series of side chain liquid crystalline polymers （SCLCPs） containing triphenylene （Tp） units in the side chains, denoted as PMTS （without spacer） and PMTnS （n = 2, 3, 4, 6, which is the number of the methylene units between the main chain and Tp moieties in the side chains）, with different lengths of spacers were synthesized through conventional free radical polymerization. The chemical structures of the monomers were confirmed by 1H/IaC-NMR, and the phase behaviors were examined by differential scanning calorimetry （DSC）, polarized optical microscopy （POM） and wide-angle X-ray diffraction （1D and 2D WAXD）. The molecular characterization of the polymers was performed with 1H-NMR, gel permeation chromatography （GPC） and thermogravimetric analysis （TGA）. The phase behaviors of the polymers have been investigated by a combination of techniques including DSC, POM, 1D and 2D WAXD. The results showed that the length of spacer has significant effects on the LC phase behavior of polymers. For PMTS and PMT2S, they displayed the columnar phase developed by the Tp moieties and the main chain as a whole due to the strong coupling effect of the Tp moieties and the main chain. For the PMT3S, PMT4S and PMT6S, they formed the symmetry hexagonal columnar （~n） phase owing to the decoupling effect. All of these indicated that the ＂decoupling effect＂ or ＂coupling effect＂ depended on the length of spacers, leading to the different LC phase formation mechanism.

Self-assembly and Properties of Block Copolymers Containing MesogenJacketed Liquid Crystalline Polymers as Rod Blocks

Mesogen-jacketed liquid crystalline polymer （MJLCP） has attracted great attention because of its rigid conformation, facile synthesis, and structural controllability. In this feature article, the self-assembly of MJLCP-based block copolymers （BCPs） is briefly reviewed, especially the nanostructures of rod-coil diblock copolymers （diBCPs）, rod-rod diBCPs, and triblock copolymers. In addition, the properties of the self-assembled BCPs are also summarized, including their applications as liquid crystalline thermoplastic elastomers and solid polymer electrolytes. The article also discusses the major challenges and future directions in the study of MJLCP-based BCPs.

Polysiloxane Side-chain Liquid Crystalline Polymers Prepared by Alkyne Hydrosilylation

We describe in this work an alkyne-hydrosilylation approach to synthesize a series of novel polysiloxane sidechain LCPs attaching end-on or side-on mesogenic side groups. Their properties are characterized by NMR, FTIR, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetty, polarized optical microscopy and small-angle X-ray scattering. These obtained alkenylsilane linked novel LCPs exhibit higher glass transition temperatures and clearing points, and especially display the tendency of forming smectic phases, in strong contrast with the nematic phases of their comparative conventional alkylsilane linked analogues, which manifests more rigid features of the alkenylsilane linkages and their significant influence on the mesomorphic properties.

NUCLEATION ACTION OF THERMOTROPIC LIQUID CRYSTAL POLYMERS IN THE BLENDS WITH PET

The present work concerns the crystallization of PET accelerated by addition of thermotropic liquid crystalline polymers (TLCP)based on two aromatic copolyesters: PHB/PET (60:40 ) and PHB/HDA/2,6-DNA /IPA ( 50:25 : 12.5 : 12.5 ). The investigation has been made by measurements of the cold-crystallization and melt-crystallization temperatures by DSC and of the changes of density and depolarizing light intensity during the isothermal process. In addition, the morphology of selectively etched surface of compressing pellets proved the presence of crystalline fibrillar structure, it can be supposed to have grown up from the micelle nucleus based on bundle of rigid TLCP chains.

Fluorescence quenching effect of metal ions for α,α'-diamine containing conjugated polymers in solid films

The fluorescence quenching effect of the conjugated polymers P1 and P2 (the molecular recognitions are twisted 2,2'-bipyridine (bpy) and planar 1,10-phenanthrolin(phen), respectively) films upon the addition of metal ions has been studied. And the results showed that P2 exhibited stronger fluorescence quenching ability upon the addition of both transition metal ions and main group metal ions compared with that of P1. The 20° twist angle between the two consecutive pyridine rings of bpy unit in the P1 main chain is the reason for the weaker fluorescence quenching ability compared with P2, in which the planar phen unit can chelate with metal ions relatively freely without the conformational transition. So P2 is a kind of material with better properties for solid film devices, such as sensors for metal ions recognition.