A literature review on the in situ generation of reinforcing fibers

Liquid crystal polymers (LCPs) are a relatively new class of materials. These polymers usually consist of rigid rodlike molecular chains and they are capable of forming highly oriented structures even in the as-made product, with strength/modulus significantly higher than those of the conventional flexible chain polymers. Blending of LCPs with conventional polymers produces composite-like structures with LCPs serving as the reinforcing component. The properties of the blends are affected by the size, shape and distribution of the LCPs in the matrix polymer, which in turn are related to the processing conditions such as the blend composition, the extrusion and drawing conditions, the viscosity ratio of the component polymers and the type and grade of the LCPs and the matrix polymers. Improved processability of the blend due to the reduction in viscosity and the improved interfacial adhesion between reinforcing fibers and the matrix polymer are among the advantages of these materials over the conventional short fiber reinforced composites. This paper gives a brief review of the work currently available in the literature on rheology, fabrication, blend morphology and mechanical/thermal properties of the in situ composites from blends of LCPs and conventional polymers.     

Chiral liquid crystalline polymers: Recent issues and perspectives

The syntheses and structures of chiral liquid crystalline polymers (LCPs) are briefly reviewed with emphasis on the established structure-property correlations. The most recent advances and future trends in their potential applications in optics and electrooptics are also outlined, with particular reference to the ferroelectric, electroclinic, piezoelectric, and nonlinear optical properties of chiral LCPs.     

Liquid Crystalline Polymers

History of Liquid Crystalline PolymersThe liquid crystalline(LC)state was first observed by Austrian botanist and chemist F.Reinitzer more than a century ago,and it was then confirmed in 1888 by German physicist O.Lehmann who named such a state of matter as"liquid crystal"in 1900.While low molecular mass(LMM)liquid crystals were successfully used in LC displays(LCDs),the development of LC polymers(LCPs)followed an independent path.Conceptually,LCPs are prepared with the incorporation of mesogenic groups that are responsible for the formation of LC mesophases,such as rod-like(calamitic)and discotic ones,into polymer chains.Depending on where the mesogens are attached,traditionally there are three major categories of LCPs.Main-chain LCPs(MCLCPs)have mesogens in the polymer backbone,while mesogens of side-chain LCPs(SCLCPs)are incorporated as side groups in a polymer with a relatively flexible main chain.In main-chain/side-chain combined LCPs(MCSCLCPs),mesogens are in both the backbone and side chains.Other classes of LCPs include mesogenjacketed LCPs(MJLCPs),dendronized LCPs,and LC networks(LCNs).     

一个判别液晶聚合物状态的新方法

伴随液晶相转变而产生的转变焓、转变熵可提供有关各相的结构、状态及有序度等信息.本文从动力学、热力学角度分析了液晶聚合物从各向同性熔体冷却时系统的热熵变化,建立了液晶聚合物升降温过程中的热熵图,提出了定量判断液晶聚合物从各向同性熔体冷却后所处状态的新方法.     

Properties of blends containing two liquid crystalline polymers

Blends containing two, wholly aromatic, naphthalene-based liquid crystalline polymers (LCPs) are studied. Experimental results show that the viscosities of the resulting blends are lower than the parent LCPs over the entire shear-rate range investigated. The orientation development following capillary flow demonstrates, that over a defined blend composition range, some blends have higher orientability than the constituent polymers. This is further manifested in the tensile and flexural properties of injection-molded specimens. A detailed analysis indicates that in the composition range where synergistic effects are observed in orientation development as well as in mechanical properties, only one glass transition temperature is detected. This suggests that “miscibility” is desirable for obtaining maximum properties in these blend systems.     

Invited Lecture. Molecular order and motion in nematogens from pulsed dynamic N.M.R. A comparative study of model compounds and parent liquid-crystal polymers

Abstract

Model compounds of semiflexible liquid-crystal polymers (LCPs), specifically deuteriated at various positions of the mesogenic units and aliphatic chains, have been studied by multipulse dynamic N.M.R. techniques. Analysis of the various experiments, employing a density-matrix treatment based on the stochastic Liouville equation, provides new information about the dynamic organization of the different systems. The results, referring to monomers and dimers, are discussed in relation to the properties of the parent LCPs.

The pronounced increase in orientational order from the monomers to the dimers can be rationalized by an intramolecular order transfer via highly extended spacers, in agreement with observations for the parent LCPs. A strong dependence of the nematic order on the parity of the spacer (even-odd effect) supports this concept. However, long-range orientational order of both model compounds is completely lost upon crystallization. Thus, despite the fact that dimers already achieve unusually high order parameters in the nematic phase, many of the exceptional properties of LCPs are restricted to systems with higher molecular weights.

Molecular motions in the model compounds occur within an extremely broad dynamic range, extending from 10^?12 s (internal reorientation) in the fast-rotational to 10^?3 s (director order fluctuations) in the ultraslow-motion regime. With respect to these dynamic properties, dimers behave like conventional monomeric liquid crystals, exhibiting much faster motions than the polymers.     

Luminescent sensors based on coordination polymers with adjustable emissions for detecting biomarker of pollutant ethylbenzene and styrene

Sensitive luminescent probes for phenylglyoxylic acid (PGA), which is a biomarker of ethylbenzene and styrene (EB/S) representing the internal dose of EB/S exposure, have been constructed on the basis of newly designed luminescent coordination polymers (LCPs). Three isostructural LCPs with different lanthanide centers were solvothermally synthesized and fully characterized. All the LCPs 1 – 3 display strong regulated emissions by the adjustable metal–organic coordination interactions. Among LCPs 1 – 3 , the fabricated LCP 2 can quantitatively detect PGA with the highest sensitivity in physiologically relevant ranges. The mechanism study of luminescent responses toward PGA further explains the excellent sensitivity and selectivity of LCP 2 for sensing PGA. The facile, accurate, fast, and recyclable sensing system relying on LCP materials provides a convenient approach for developing sensing platforms with adjustable emissions for assessment of the intoxication level of EB/S.     

甲壳型液晶高分子的构筑、自组装及其功能化

甲壳型液晶高分子的发展很大程度上依赖于聚合物自组装的发展,而各种可设计、可预测、可调控的自组装策略的涌现,将甲壳型液晶高分子研究推向前所未有的高度,同时也极大地丰富了高分子化学与物理的内容,提升了研究水准.研究表明,侧链"甲壳效应"在调控甲壳型液晶高分子有序结构等方面有着重要作用.本综述从甲壳型液晶高分子设计合成、液晶相态调控、嵌段共聚物自组装和功能化应用等方面,总结和评述了近年来该领域国内的最新研究进展.最后,本综述总结了甲壳型液晶高分子在发展中所面临的主要问题,并对其发展趋势进行了展望.     

Liquid crystalline polymers at interfaces

Main chain liquid crystalline polymers (LCPs) at solid-nematic interfaces exhibit a variety of phase transition between distorted and undistorted states. In one case the transition results from the confinement of grafted chains immersed in a nematic solvent and subject to homeotropic anchoring. The general features of the transition are similar for long and for short chains. The detailed physics is different since long chains exhibit Gaussian, entropic elasticity while the elasticity of the short chain is due to their rigidity. As a result it is possible to weakly confine long chains without triggering a distortion while for short chains the nematic distortion occurs simultaneously with the buckling of the rod like LCPs. Related effects are found for uniformly adsorbed LCPs and for free, confined chains. Different scenarios are expected when homogeneous anchoring is imposed.     

A Facile Strategy for the Development of Recyclable Multifunctional Liquid Crystal Polymers via Post-Polymerization Modification and Ring-Opening Metathesis Polymerization

Post-polymerization modification (PPM) offers a versatile approach for engineering multifunctional polymers, but this advantage has not been fully exploited to fabricate multifunctional liquid crystal polymers (LCPs). Here, we design a facile synthetic approach towards multifunctional LCP by combining the ring-opening metathesis polymerization (ROMP) with PPM, in which ROMP helps to prepare a reactive LCP precursor with high molecular weight, and PPM provides a facilitation to introduce functional groups into the precursor. Consequently, a photo- and humidity-responsive linear LCP (LLCP) is demonstrated to show the potential of this synthetic strategy to diversify functions of the LCPs. Under light irradiation and humidity changes, the deformation modes of the LLCP films are converted to complex shapes (bending, twisting, and curling). The obtained dual-responsive LLCP with high molecular weight possesses excellent processability and recyclability, making it possible to construct 3D shape actuators with programmable deformation behaviors under light/humidity.     

Thermally stimulated current and DSC studies of the broadened glass transition in liquid crystalline polymers

The high sensitivity of the thermally stimulated current, thermal sampling (TS) method is emphasized in a study of the breadth of the glass transition in several liquid-crystalline polymers (LCPs). Differential scanning calorimetry (DSC) was performed on all samples to further quantify the glass transition regions. For “random” copolyester LCPs with widely varying degrees of crystallinity, including highly amorphous samples, very broad glass tran-sition regions were observed. One semicrystalline alternating copolyester and a series of semicrystalline azomethine LCPs were studied as examples of structurally regular polymers. These exhibited relatively sharp glass transitions more comparable to ordinary isotropic amorphous or semicrystalline polymers. The broad glass transitions in the random copolyesters are attributed to structural heterogeneity of the chains. In one example of a moderate-crystallinity random copolyester LCP (Vectra), glass transitions ranging up to ca. 150°C in breadth were determined by the thermal sampling (TS) method and DSC. In other lower crystallinity copolyester LCPs, the main glass transition temperature as determined by DSC was comparable to that determined by TSC although cooperative relaxations of a minor fraction of the overall relaxing species were detected well below the main T_g, by the TS method and not by DSC. Rapid quenches from the isotropic melt to an isotropic glass were possible with one LCP. The anisotropic and isotropic glassy states for this LCP were found to have the same breadth of the glass transition as was determined by the TS method, although TSC and DSC show that T_g is shifted downward by ca. 15°C in the anisotropic glass as compared to the isotropic glass. © 1993 John Wiley & Sons, Inc.     

X-ray microscopy of novel thermoplastic/liquid crystalline polymer blends by mechanical alloying

Incorporation of liquid crystalline polymers (LCPs) into commodity polymers remains a challenge in the design of high-performance, low-cost polymeric blends. Blends of a thermoplastic polymer and a nematic LCP are produced here by mechanical alloying. Functionality sensitive X-ray microscopy reveals LCP dispersions as small as 100 nm in diameter. Intimate mixing remains upon subsequent melt processing, indicating that mechanical alloying is suited for applications such as recycling.     

A tensor model of liquid crystalline polymers: application to basic disclination processes

One of the features of liquid crystalline polymers (LCPs) is their strong elastic anisotropy, which means they have unequal elastic constants. Elastic anisotropy plays a crucial role in the microstructure and macroscopic properties of LCPs. In this paper, the effect of unequal elastic constants on microstructure is investigated without an external field by using a deterministic tensorial approach. In this model, the evolution of the director field can be viewed as a process driven towards the state of zero elastic torque. A tensor expression of the elastic torque is used so that the nematic symmetry is automatically conserved. In simulations of bulk samples, disclination lines of strength half and escaped integer disclinations are observed. The distortion fields around the disclinations are found to depend on elastic anisotropy. If the twist constant is the lowest, as is the case for main chain liquid crystalline polymers, the disclination lines are predominantly of the twist type.     

全芳香族热致液晶聚合物与热塑性树脂聚砜的原位复合材料

用自制的四种全芳香族热致液晶聚合物ＢＰ ＬＣＰ、ＢＰＭ ＬＣＰ、ＢＰＡ ＬＣＰ、ＢＰＳ ＬＣＰ与热塑性树脂聚砜（ＰＳＦ）熔融共混，制备了一系列原位复合材料．研究了所得材料的微观形态、热性能、力学性能等，结果显示：四种液晶聚合物中，ＢＰ ＬＣＰ，ＢＰＳ ＬＣＰ在所用加工条件下可在ＰＳＦ中取向成纤，而且这两种共混物断面上存在皮 核效应；ＢＰＭ ＬＣＰ和ＢＰＡ ＬＣＰ未成纤，均以球状存在于ＰＳＦ中．这四种液晶聚合物与ＰＳＦ的相容性较差，各共混物的Ｔｇ均分别接近于二纯组分的Ｔｇ值，ＳＥＭ照片上明显的相界面也能说明以上问题．液晶聚合物对ＰＳＦ有增强作用，但增强效果不很显著，这可能是二者相容性较差所致     

A tensor model of liquid crystalline polymers: application to basic disclination processes

One of the features of liquid crystalline polymers (LCPs) is their strong elastic anisotropy, which means they have unequal elastic constants. Elastic anisotropy plays a crucial role in the microstructure and macroscopic properties of LCPs. In this paper, the effect of unequal elastic constants on microstructure is investigated without an external field by using a deterministic tensorial approach. In this model, the evolution of the director field can be viewed as a process driven towards the state of zero elastic torque. A tensor expression of the elastic torque is used so that the nematic symmetry is automatically conserved. In simulations of bulk samples, disclination lines of strength half and escaped integer disclinations are observed. The distortion fields around the disclinations are found to depend on elastic anisotropy. If the twist constant is the lowest, as is the case for main chain liquid crystalline polymers, the disclination lines are predominantly of the twist type.     

Alkyl-chain branched effect on the aggregation and photophysical behavior of polydiarylfluorenes toward stable deep-blue electroluminescence and efficient amplified spontaneous emission

The control of the condensed superstructure of light-emitting conjugated polymers(LCPs) is a crucial factor to obtain high performance and stable organic optoelectronic devices.Side-chain engineering strategy is an effective platform to tune inter chain aggregation and photophysical behaviour of LCPs.Herein,we systematically investigated the alkyl-chain branched effecton the conformational transition and photophysical behaviour of polydiarylfluorenes toward efficient blue optoelectronic devices.The branched side chain will improve materials solubility to inhibit interchain aggregation in solution according to DLS and optical analysis,which is useful to obtain high quality film.Therefore,our branched PEODPF,POYDPF pristine film present high luminance efficiency of 36.1% and 39.6%,enhanced about 20%relative to that of PODPF.Compared to the liner-type sides' chain,these branched chains also suppress chain planarization and improve film morphological stability effectively.Interestingly,the branched polymer also had excellent stable amplified spontaneous emission(ASE) behaviour with low threshold(4.72 μJ/cm~2) and a center peak of 465 nm,even thermal annealing at 220 C in the air atmosphere.Therefore,side-chain branched strategy for LCPs is an effective means to control interchain aggregation,film morphology and photophysical property of LCPs.     

Molecular dynamics and ordering of side chain liquid crystal polymers as studied by paramagnetic resonance

Abstract

Molecular dynamics of side chain liquid crystalline polymers (LCP) and their components were studied using the technique of paramagnetic resonance. A cigar shape spin probe (COL) and a nearly spherical spin probe (TPL) were used to study the motions and order of the LCPs. Computer simulations of the observed spectra were performed. Both rotational correlation times and order parameters were extracted from these simulations. We found that LCPs containing 30 per cent and 50 per cent of mesogenic side chains had about the same viscosity as indicated by nearly equal tumbling times at the same temperature. In addition, the LCPs motion is considerably slower than that of the monomeric liquid crystal indicating that the spacer couples the motions of the side chains to those of the main chain. Rotations about axes perpendicular to the side chain are slowed more than rotations about an axis parallel to the side chain. DSC measurements were employed to study the phase transitions. The 30 and 50 per cent LCPs displayed first order NS_A transitions, but the 50 per cent LCPs transition was much weaker, in agreement with McMillan's theory which predicts a first order transition for T _NS/T _NI>0.87 (observed ratios are 0.98, 0.90 and 0.86 for 30, 50 and 100 per cent LCPs, respectively). The 30 per cent LCP has a very short nematic range so that the nematic order, which is not saturated at the NS transition, can couple with the smectic order. This was indicated by a sharp change in slope of the order parameter versus temperature plot as the smectic is entered. The LCPs studied formed a highly ordered glass when cooled in a 1 T field. If one could find a LCP with similar ordering properties whose glass temperature is well above room temperature, then one would have a useful binder for the manufacture of haze-free polymer dispersed liquid crystal displays.     

Alkyl-chain branched effect on the aggregation and photophysical behavior of polydiarylfluorenes toward stable deep-blue electroluminescence and efficient amplified spontaneous emission

Robust branched polydiarylfluorenes are constructed forstable deep-blue electroluminescence and efficient amplified spontaneous emission.     

Capillary and slit-die flow of two liquid-crystalline polymers. The effect of pressure on viscosity

Viscosity measurements on two commercial thermotropic liquid crystalline polymers (LCPs) (a copolyester and a polyesteramide) were performed using both capillary and slit die methods. The results are in agreement with those presented in the literature for the same LCPs, when the measurements are carried out with a L/D = 30 die; these results are affected more by Bagley corrections for the polyesteramide than for the copolyester. For both LCPs, viscosities measured in the slit die are lower than those obtained by capillary rheometry. Nevertheless, the difference is much bigger in the case of the polyesteramide, for which a reduction by a factor of 3 is observed. This is not due to the preshear or thermal history, since the same piston-barrel system and thermal treatment were applied in both types of measurements. Depending on the polymer sample and temperature, concave and convex curvatures were observed in the pressure profiles during the slit flow. From these curvatures, the pressure coefficient α of viscosity was evaluated. However, in the case of the polyesteramide the convex curvature leads to a negative coefficient (the viscosity decreases with pressure, instead of increasing). This result may be explained by envisaging a change in the structure of the melt along the slit length. © 1993 John Wiley & Sons, Inc.     

Optical and mesomorphic properties characterisation of chiral liquid crystalline copolysiloxane exhibiting cholesteric and blue phases

A series of liquid crystalline polymers (LCPs) have been synthesised by two cholesteric monomers M₁, M₂ and a nematic monomer M₃. The chemical structures and liquid crystalline properties of the monomers and polymers have been characterised by FTIR, ¹H-NMR, differential scanning calorimetry, thermogravimetric analyses, X-ray diffraction measurements and polarising optical microscopy. All LCPs show a high thermal stability with wide mesophase temperature ranges. For polymer P₁ bearing only cholesteric LC monomers component, it shows a cholesteric phase, whereas others display a blue phase besides a cholesteric phase. The formation of the blue phase is based on the structures of the polymers and the produced biaxial helix. The glass transition temperature and isotropic temperature of the polymers decrease on heating cycle with increasing the content of M₃ in the polymers. The specific rotation values of the polymers are temperature-sensitive. The reflection spectra of polymers P₁–P₆ show that the maximum reflected wavelengths shift to long wavelength with increasing the content of M₃ in the polymer systems. The frequency and intensity of the bands change sharply at the temperature where cholesteric phase changes to blue phase, but they show a weak dependence on temperature in the blue phase.