Spectroscopic investigation of local molecular dynamics in liquid crystals II. Polymers

In the analysis of spectroscopic data from liquid crystals consisting of either small molecules or polymer chains, it is essential that account be taken of some particular features due to the oriented nature of the phases investigated. For liquid crystal polymers some specific additional problems arise, such as the difficulties in orienting main-chain liquid crystal polymers, the occurrence of the glass-liquid transition and secondary transitions. These questions are first discussed, then the studies performed using ²H and ¹³C N.M.R., E.S.R. and dielectric relaxation on both side-chain and main-chain liquid crystal polymers are presented.     

侧基甲壳效应和甲壳型液晶高分子

侧链液晶高分子体系里,液晶基元可以通过尾接或腰接的方式与主链相连.一般认为,在液晶基元与主链间插入一段长度合适的＂柔性间隔基＂可有效实现主、侧链间的动力学去偶合,从而有利于侧基液晶基元之间的有序排列.作为一类特殊的腰接型侧链液晶高分子,甲壳型液晶高分子中体积较大的侧基（如棒状液晶基元）通过非常短的间隔基或仅通过一个碳-碳键直接横挂至主链上,这导致了强烈的甲壳效应,使得主链被迫伸展.因此,可从与＂柔性间隔基＂完全不同的角度出发,充分利用主链和侧基间的偶合作用,设计甲壳型液晶高分子.本文综述了腰接型侧链液晶高分子中的侧基甲壳效应、甲壳型液晶高分子中由主链与侧基相互作用所导致的特殊构象以及液晶相结构.研究表明,侧基甲壳效应在调控甲壳型液晶高分子的形状、尺寸以及螺旋结构等方面有重要作用.甲壳型液晶高分子可作为刚-柔嵌段共聚物的刚性链段,也可作为主/侧链结合型液晶高分子的主链部分参与到多层次分级超分子有序结构的构筑之中.     

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.     

偶氮型液晶高分子的研究及应用

偶氮液晶高分子由于其具有特殊的光致异构和光致变色等光学性质,在光信息贮存材料、光开关材料和非线性光学设备材料等领域具有巨大的应用潜力,近年来得到了国内外研究者的广泛关注。本文概述了偶氮型液晶高分子的结构特征,详细介绍了主链型偶氮液晶高分子、侧链型偶氮液晶高分子、树枝状偶氮液晶高分子以及星型偶氮液晶高分子的研究现状及在光储存、光开关及光调制偏振片等方面的应用进展,指出了存在的问题和研究方向。     

Regio-regular and cross-conjugated poly(thienylene vinylene)s through acyclic diene metathesis

Poly(thienylene vinylene)s (PTV's) are early examples of conjugated polymers but have not been extensively studied when compared with closely analogous polythiophenes. PTV's synthesized through previously reported techniques are similar in structures that contain various alkyl or alkoxy side-chains that exert limited impact on the polymer electronic properties. Herein, we report the preparation of a series of regio-regular PTV's (rr-PTV's) bearing cross-conjugated side-chains through ADMET polymerization of a common brominated di(thienylene vinylene) (DTV) monomer followed by PPM reactions on the resulting brominated PTV. These new polymers contain a bulky silyloxy alkyl side-chain and a functionalized thiophene moiety on every main-chain thiophene unit, and their regio-regular placement is confirmed by NMR spectroscopy. The thienyl based side-groups broaden polymer absorption ranges and at the same time lead to uncommon emission properties that are results of light-induced charge transfer events between the polymer main-chains and side-chains. Removal of the silyl groups on one of these rr-PTV's led to insoluble materials and x-ray diffraction experiments on the collected solids displayed distinct scattering peaks that are absent from similarly functionalized regio-random PTV's reported previously, thus suggesting better crystallinity originated from regio-regularity.     

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     

Linear polyesters containing isocyanurate rings

Two series of linear polyesters containing isocyanurate rings have been prepared to determine the effect of structural variations on thermal and solubility properties. The polyesters were prepared by the polycondensation reaction of isocyanurate containing difunctional acid and ester monomers with linear diols. The substituent on the isocyanurate ring and the length of the acid side chain have been shown to have considerable effect on the glass transition temperature T_g. Different solubility properties were observed for the series of polyesters in which the pendant substituent was ? C₆H₅ and the acid side-chain was ? CH₂CO₂H. These polymers were insoluble in THF, and the polyester prepared from 1,6-hexanediol was also insoluble in chloroform. Thermal gravimetric analysis (TGA) indicated that structural differences had no significant effect on the thermal stability of these linear polyesters.     

一种手性甲壳型液晶高分子的稀溶液行为及链刚性

用激光光散射和粘度法研究了一系列窄分子量分布的新的手性甲壳型液晶聚合物P1～P6的溶液行为及其链刚性.研究发现四氢呋喃是聚合物P1～P6的良溶剂.在四氢呋喃溶液中,聚合物P1～P6的特性粘数[η]和均方根旋转半径z12对重均分子量Mw的依赖关系分别是[η]=(2.75±0.05)×10-3Mw0.78±0.02和z12=(1.53±0.04)×10-2Mw0.60±0.01.按照YamakawaFujiiYoshizaki蠕虫状圆筒模型的粘度理论和BohdaneckyBushin表达式,求得聚合物的单位围长摩尔质量ML=(29.8±1.0)×102nm,构象保持长度q=(15.4±3.0)nm.q和MHS方程指数α的值说明这类在结构上属于侧链型液晶高分子的聚合物在良溶剂四氢呋喃中呈现比较伸展的刚性链构象,其链刚性与半刚性主链液晶高分子的相似.     

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 isotropi-zation and liquid-crystallization transitions were studied by means of polarizing microscopy. These tran-sitions were found to be composed of the initiation of a new phase at local places of the old phase matrix andthe growth of the new phase domains. The kinetics of the liquid-crystallization of the polymer from anisotropic melt to a smectic mesophase was also investigated. The isothermal process of the transition can bedescribed by the Avrami equation. The values of the Avrami exponent were found to be around 2.6, which islower than the value usually obtained for crystallization transition of polymers, but larger than that reportedfor liquid-crystallization transition of main-chain polymers. These results may indicate the difference ingrowth geometry of new phase during transition between crystallization and liquid-crystallization in generaland 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 hightransformation rate similar to that of main-chain polymers and small-molecule liquid crystals, while thecrystallization of polymers can only proceed at large undercoolings. These phenomena can be explained bythe idea that the surface free energy of nucleus during liquid-crystallization transition is less than that forcrystallization, and evidence was obtained from analysis of the temperature dependence of the transformationrate.     

Liquid-crystalline ionomers

Liquid-crystalline (LC) ionomers combine the properties of ionomers (cluster formation of the ionic groups) with LC phases. They can be prepared with LC main-chain and LC side-chain polymers.     

Molecular design and synthesis of novel side-chain liquid crystalline polymers

Novel side-chain liquid crystalline polymers were synthesized based on the molecular design of the chemical structures of main-chain, spacer, and mesogenic groups. The main-chain structures are polyether, by the cationic ring-opening polymerization of oxetane derivatives, and polydiene, by the radical polymerization of diene derivatives. Some of the polymers from oxetanes with various mesogen and spacer groups show smectic liquid crystalline phase. Both cyano- and fluorine-substituted biphenyls are good mesogenic groups in these liquid crystalline polymers. Polydiene also acts as a novel main-chain to give smectic liquid crystalline state with cyanobiphenyl or fluorobiphenyl as a mesogen. Not only oligomethylene groups but also siloxane and oligo(oxyethylene) groups act as a component of the spacer groups to give liquid crystalline state.     

Side-chain liquid crystalline polyesters derived from diethylmalonate and/or 1,3-propanediol

A series of azo monomers for polycondensation have been synthesized and characterized. These monomers, which contain electron-donor or acceptor substituents, have been condensed with aliphatic monomers to obtain two different series of aliphatic main-chain polyesters with pendant mesogenic groups. The polymers display nematic or smectic phases depending on the structural modifications of pendant mesogenic groups and the length of the flexible main-chain. In addition to these series, two polyesters with a high concentration of side pro-mesogenic groups have been synthesized. © 1996 John Wiley & Sons, Inc.     

Synthesis and properties of two new series of isomeric liquid crystalline polyesters with conjugated double bonds

Two homologous series of flexible main chain liquid crystalline polyesters with isomeric mesogenic groups containing conjugated double bonds, were synthesized and studied by differential scanning calorimetry and optical microscopy. One series (S1) has the p-phenylene-diacryloyloxydibenzoyl moiety as a mesogenic unit. The other (S2) has the terephtaloyl dioxydicinnamoyl moiety as a mesogenic unit. The reactivity of the conjugated double bonds of the p-phenylenediacryloxy unit, at the temperature of mesophase formation, impedes the stability of liquid crystalline mesophases of polymers of series (S1). Two low molecular weight analogues of polymers were also prepared and their properties compared with those of polymers of similar structure. The two model compounds form stable smectic mesophases over a wide range of temperatures, which shows the high mesomorphogenic ability of both mesogenic units.     

Relaxation processes in oriented liquid crystalline polymers

A review is presented of research on oriented thermotropic liquid crystalline polymers undertaken at Leeds University. A range of main-chain polyesters has been studied based on 1,4-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid as the primary monomers. By using a combination of dynamic mechanical, dielectric and NMR measurements insight has been gained into the molecular motions associated with the three principal relaxation processes. The behaviour in tension, for stresses parallel and perpendicular to the principal orientation direction, has been related to that in shear by use of mechanical models.     

NMR Investigation of the Main-Chain Orientation in Liquid-Crystalline Side-Chain Polymers

The main-chain orientation in different groups of liquid-crystalline side-chain polymers was investigated using several NMR techniques. For two polyesters the average orientation of the main chain in dependence on the main-chain spacer length could be found from 2D PASS experiments. In polysiloxanes with different mesogenic side groups and different spacer lengths this information could be received from chemical shift anisotropy measurements. Additionally, application of a modified β-echo allowed the separation of the dipolar ²⁹Si-²⁹Si interaction and to characterize the transversal anisotropy of the main-chain segments. Comparison with small angle neutron scattering results gave good agreement, where the different length scale of both methods has to be taken into account.     

Influencing factors on liquid crystalline properties of cholesterol side-chain liquid crystalline polymers without spacer: molecular weight and copolymerisation

ABSTRACT

It is a challenge to tailor the phase behavior and phase structure of side-chain liquid crystalline polymers carrying targeted ordered structures and functional properties. In this work, liquid crystalline (LC) properties of cholesterol side-chain polymers without spacer were controlled by molecular weight (M_n) and copolymerization. On the one hand, two series of homopolymers without the spacer, poly (methacrylic acid) cholesterol esters (PCholMC_n) and poly (acrylic acid) cholesterol esters (PCholAC_n) with different M_n and low polydispersity, were achieved by reversible addition-fragmentation chain transfer polymerization. The experiment results indicated that the M_n had little effect on the LC properties of PCholMC_n and all homopolymers formed the smectic A phase. However, the phase structures of PCholAC were found to be strongly M_n dependent. The polymers PCholAC_n were amorphous when the M_n was lower than a critical value of approximately 1210₃ g/mol. But when the M_n exceeded the critical value, the polymers exhibited smectic A phase. On the other hand, two kinds of random copolymers, poly(cholest-5-en-3-methacrylate)-co-polymethyl acrylate (PCholMC-co-MA) and poly(cholest-5-en-3-acrylate)-co-polymethyl acrylate (PCholAC-co-MA) were synthesized with various composition. The findings suggested that the steric effect of main-chain and the interaction of mesogens would promote the formation of LC phase.     

Main chain thermotropic polyesters having flexible spacers—influence of ester group linking order between mesogenic unit and flexible spacer

Two series of main chain thermotropic polyesters having a decamethylene spacer were prepared and their thermal transitions and liquid crystalline properties were studied. The linking sequence of the ester bond between the mesogenic unit and spacer, i.e., versus with M and S being mesogenic unit and spacer, respectively, was found to influence profoundly the nature of the mesophase formed by the polymers. The former favors the formation of a smectic phase, while the latter favors the formation of a nematic phase. The structure of the central dicarboxylic acid moiety of the triester mesogenic units also was found to influence greatly the polymer's ability to form mesophases.     

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.     

Charge-transfer complexing in polymer mixtures. IV. Acceptor polymers from nitrophthalic acids and their mixtures with donor polymers from aryliminodiethanols

A series of electron acceptor polyesters was prepared from 5-nitroisophthalic, nitroterephthalic, and 4,6-dinitroisophthalic acids. Those polymers prepared at high molecular weight were tough, soluble, linear materials of well-defined structure. These materials were mixed with electron-donor polymers based on aryliminodiethanols where the aryl group was phenyl, p-anisyl, 2,5-dimethoxyphenyl, and 3,4,5-trimethoxyphenyl. The effects of the mixtures on the mechanical, spectral, viscometric, and conductive properties were studied and compared to the component polymers.     

Synthesis and structure of wholly aromatic liquid–crystalline polyesters containing meta- and ortholinkages

Wholly aromatic main-chain rigid-chain polymers containing meta- and orthokink linkages were synthesized. The thermal property, liquid crystallinity, and crystalline structure were studied using DSC, polarized light microscopy, and wide-angle X-ray scattering. These polymers exhibited liquid crystallinity up to 50 mol % of meta- and orthokink linkages. The existence of liquid crystallinity in these polymers may be attributed to the adoption of cis conformation in kink units in these polymers because the energy penalty for doing so can be compensated by the formation of the liquid–crystalline phase. The crystallinity of the polymers was low, and the crystal structure was quite similar to that of the pure polymers (without kink units). This can be explained by that fact that the crystal region mainly consists of the nonkink units, and the kink units disrupt the crystallization of the polymers and form defects. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1242–1248, 2001