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.     

刚棒中心含侧基的刚棒-线团分子的合成及聚集体结构分析

合成了一系列三嵌段刚棒-线团分子,这些分子由含有苯、联苯和具有侧基的苯单元与聚合度为7,12及17的不同长度烷氧基链组成.通过氢核磁共振仪(1H NMR)和质谱(MALDI-TOF MS)对其结构进行了表征,利用差示扫描量热法(DSC)、偏光显微镜(POM)和小角X射线散射实验(SAXS)对这些液晶化合物的自组装行为进行了研究.实验结果表明,侧基含酯基的分子1a~1c自组装成层状、倾斜柱状和六方穿孔层状结构;而侧基含羧基的分子2a~2c则自组装成倾斜柱状、体心四方聚集体.可见,随着烷氧基链长度的改变,刚棒中心的羧基和酯基能诱导分子的自组装行为发生变化.     

刚柔三嵌段共聚物的柱状结构构筑

合成了以酯键和醚键相连的苯和联苯作为刚棒B嵌段,以聚合度为7,12和17的聚环氧乙烷为A嵌段及辛基或十六烷基为C嵌段的ABC型三嵌段线团-刚棒-线团分子.通过核磁共振氢谱和基质辅助激光解吸电离时间飞行质谱(MALDI-TOF MS)对其结构进行了表征,利用偏光显微镜(POM)、示差扫描量热法(DSC)和小角X射线散射实验(SAXS)对其本体状态下的自组装行为进行了研究.结果表明,聚环氧乙烷聚合度为7、烷基链分别为辛基和十六烷基的化合物1a和2a在固相和液晶态分别自组装成倾斜柱状结构和矩形柱状结构,而具有长聚环氧乙烷链的化合物2b、2c和1c在固相都自组装成倾斜柱状结构.发现聚环氧乙烷链和烷基链的长度显著地影响线团-刚棒-线团分子体系的自组装行为.通过改变线团-刚棒-线团分子体系中柔性链长度的策略,可以精确地调控刚柔三嵌段共聚物的聚集体结构.     

基于“多链超分子柱”的侧链液晶高分子柱状相

一些具有伸展构象的侧链液晶高分子,如甲壳型液晶高分子或树枝化高分子,可以经由分子链的平行排列而呈现柱状液晶相.一般认为,该类柱状相的基本结构单元是单根高分子链所形成的超分子柱.而以几根链组装形成的超分子柱,即"多链超分子柱",也可作为侧链液晶高分子柱状相的基本结构单元,但多年以来这一现象并未引起人们的重视.近期,我们以hemiphasmid型侧链液晶高分子为研究对象,阐明了"多链超分子柱"是侧链液晶高分子柱状相微相分离的一种重要形式.本文从hemiphasmid型侧链液晶高分子的柱状相结构分析、化学结构对"多链超分子柱"的影响、"多链超分子柱"模型的理论分析与预测、"多链超分子柱"的"柱内缠结"以及hemiphasmid型侧链液晶聚降冰片烯的功能性等若干方面,对基于"多链超分子柱"的侧链液晶高分子柱状相进行了介绍.我们认为,深入研究"多链超分子柱"性质,将拓展侧链液晶高分子的应用领域,加深对高分子物理基本问题的认识.     

液晶二聚体

液晶二聚体作为半柔性主链型液晶聚合物的简化模型, 通过对其液晶性质的研究, 有助于理解更复杂聚合物体系的液晶行为. 另外, 液晶二聚体作为一类特殊的液晶也有其自身的相结构和相行为. 以分子结构与液晶态的相互关系为主线, 系统介绍了目前文献报道的对称及非对称棒状液晶二聚体(线形、H形、U形、T形)、盘状液晶二聚体(对称的盘-盘状液晶二聚体和非对称的盘-棒状液晶二聚体)和香蕉形液晶二聚体(对称的香蕉-香蕉形液晶二聚体和非对称的香蕉-棒状液晶二聚体)等各种不同类型的液晶二聚体的研究进展, 以期为新型液晶二聚体的分子设计提供一些借鉴.     

单取代侧链液晶聚炔的相结构

侧链液晶聚炔由于具有潜在的导电性能和液晶性能而得到越来越多的关注。本文综述了单取代侧链液晶聚炔主链的立体构型与构象及形成的柱状相结构、近晶相、溶致液晶相及外场中形成的相结构。旨在介绍主链构象、间隔基长度、液晶基元的结构和尾链长度等因素对其相结构的影响。     

线团-刚棒-线团三嵌段分子有序纳米结构的自组装

目前,在纳米科学和仿生化学等方面的一个非常吸引人的课题是构建一种新颖的、复杂的大分子或超分子体系,并通过设计连接有机嵌段单元使其具有很好的形状和功能。在线团一刚棒一线团三嵌段分子体系中,刚棒嵌段的各向异性和连接嵌段的微相分离作用导致分子自组装形成各种有序聚集体,并且通过改变柔性链体积分数、分子长度、柔性链横截面积、刚棒...     

甲壳型液晶高分子的化学结构及其与性能间关系的研究

设计并合成了7种新型甲壳型液晶高分子,研究了液晶基元的化学结构和立体效应对单体及其聚合物液晶性的影响.发现在液晶基元的末端引入极性或可极化的原子基团提高了单体的熔点和液晶相的热稳定性;液晶基元的长径比越大,单体的熔点和清亮点越高;聚合使单体的液晶稳定性增加、液晶相温度范围变宽;侧链液晶基元的极性、刚性和空阻越大,聚合物的玻璃化温度越高;酰胺基团无论是在分子的末端还是在连接部位,都使单体的熔点和聚合物的玻璃化温度提高,但在分子末端时液晶相较稳定,作为中心桥键时不利于液晶相的稳定形成.     

新型棒状苯基咪唑苯酯类化合物的合成及其液晶性能研究

以Ullmann偶合反应为关键步骤, 合成了带端氧基链的苯基咪唑苯酯系列化合物, 采用偏光显微镜(POM)、差示扫描量热仪(DSC)及X衍射等手段研究了其液晶行为. 研究表明, 通过改变末端烷氧基链的长度及数目, 这类分子可组装形成向列相(N)和层列相(SmA)等液晶相态, 但随着烷氧基链数目的增多, 这类分子的液晶相消失, 初步找出了这类化合物结构与液晶性能间的关系, 通过对相关化合物的单晶X衍射结构及其液晶相的2D-X衍射测试结果的分析得出, 这类化合物通过分子自组装形成的层列相具有双分子层状结构(SmA₂).     

含1,3,4-噁二唑甲壳型液晶聚合物的合成与表征

甲壳型液晶聚合物（mesogen-jacketed liquid crystal polymer,MJLCP）是1987年由周其凤教授[1]首先提出的概念.从化学结构看,甲壳型液晶聚合物属于侧链型,由烯类单体经链式聚合制得,容易得到高分子量的产物,具有一般柔性侧链型液晶聚合物的一些优点.但是与柔性侧链型液晶聚合物不同的是,MJLCP分子中的刚性液晶基元是通过腰部或重心位置与主链相联结的,在主链与刚性液晶基元的侧基之间只有很短或者没有柔性间隔基.由于在这类液晶聚合物的分子主链周围空间内刚性液晶基元的密度很高,分子主链被由液晶基元形成的外壳所包裹并被迫采取相对伸直的刚性链构象.因此,这类液晶聚合物又和主链型刚性链液晶聚合物相似,具有较明显的链刚性.近年来,周其凤课题组围绕甲壳型液晶聚合物深入开展了分子设计与合成、分子结构与性能等多方面的研究.其中,设计合成具有特定功能的甲壳型液晶聚合物是在以往研究工作和学科交叉融合的基础上发展起来的一项新的研究工作.将一些有特殊功能的基团引入到甲壳型液晶聚合物中会使其具有崭新的特性.     

Distinct columnar and lamellar liquid crystalline phases formed by new bolaamphiphiles with linear and branched lateral hydrocarbon chains

A universal building block for the convergent synthesis of a wide variety of different T-shaped ternary amphiphiles was developed and used for the synthesis of a series of new liquid-crystalline materials composed of a rigid biphenyl core with polar glycerol groups at both ends and linear or branched alkyl chains in a lateral position. In addition, compounds with bulky achiral (2,4,6-trimethylphenoxy, adamantane-1-carboxylate, benzoate) or chiral (menthyl or cholesteryl) substituents attached to the end of the lateral alkyl chain were also investigated. In all cases the lateral chains were connected to the aromatic core by an ether linkage. The effect of the ether linking unit on mesophase stability and mesophase type is discussed with respect to conformational effects. The liquid-crystalline phases were investigated by polarizing microscopy, calorimetry, and X-ray diffraction of surface aligned samples. Upon enlarging the lateral chains a series of different polygonal cylinder phases was observed, which were replaced by lamellar phases and a non-cylinder hexagonal columnar phase by further increasing the size of these substituents. Remarkably, only pentagonal, hexagonal, and giant hexagonal cylinder phases could be observed, whereas mesophases composed of cylinders with a smaller number of sides are missing. No distinct chirality effects were observed for the menthyl- and cholesteryl-substituted compounds. However, the rodlike shape of the polycyclic cholesteryl core leads to a unique phase structure combining an organization of the alicyclic cholesteryl cores perpendicular to the layer planes and the aromatic biphenyl cores parallel to the layer planes.     

Unusual thermal behaviour of mesogens containing an N,N-dialkylaminomethylene lateral substituent

An N,N-dialkylaminomethylene lateral substituent can be used to reduce the melting temperatures of nematogens having a long rigid core. However, compared with a single lateral alkoxy chain, this lateral substituent does not enhance the thermodynamic stability of the mesophase. DSC curves and optical microscopy show that after melting, a new solid appears in the liquid crystal phase or in the isotropic phase of these compounds. NMR spectra of the nematic phase and of the solid phase show that a thermal reaction releases dialkylamine into the medium and produces a disubstituted 2 H -indazole in rather good yield. Further heating of each individual mixture leads to a second wide range enantiotropic nematic phase. The purified disubstituted 2 H-indazole has a larger nematic range and the nematic phase is stable at high temperature, indicating that the 2 H -indazole motif can be used to build new mesogenic structures. The temperature dependence of the 13C chemical shifts of one of the initial compounds was obtained. The results indicate that the two chains on the nitrogen atom are equivalent and more or less folded back in the same way along the mesogenic core.     

不同拓扑构型嵌段液晶分子的合成与相变行为

本文对近来报道的三类嵌段液晶分子：多羟基1－苯甲酰胺－2,3－丙二醇两亲性分子I,星状季戊四醇苯甲酸酯II及带侧链的波拉化合物III的合成及自组装行为作了综述。这些分子由各向异性嵌段、两亲性嵌段和烷基链（或全氟链）以不同的拓扑形式组合而成,其合成的关键步骤是Pd(0)催化下碘代全氟烷烃对双键的自由基加成反应以及Pd(0)催化的偶合反应。通过调节亲水部分和亲脂部分的比例, 在I和II-F中观察到了从近晶层相（Sm）到柱相（Col）再到三维立方相（Cub）的液晶相序列;在波拉分子III-F中通过改变侧链的长度, 获得了一系列柱相及新型层相。这些研究表明, 利用多元化竞争组合理念,将分子中不相容的部分以不同的拓扑形式结合在一起,通过它们的微观相分离, 形成不同的微观区域, 获得不同的界面, 产生不同的界面曲率, 可设计合成具有不同微观结构的超分子体系, 从而在分子水平上控制分子的自组装行为; 同时全氟链的引入所带来的氟效应能促进微观分离,稳定液晶相,并有利于复杂超分子体系的产生。     

Influence of peripheral alkyl chain length on the mesomorphic behaviours of hexasubstituted triphenylene 2,3-dicarboxylic esters

A comparative study of our established synthetic approaches to hexasubsituted triphenylenes 2,3-dicarboxylic esters containing four identical β-alkoxy and two adjacent β-alkoxycarbonyl side chains shows that the phase behaviours of small-sized discotic liquid crystals can be tailored over a wide range by simply varying the length of the peripheral alkyl chains. All the prepared esters in two series were observed to form a single hexagonal columnar phase, except for Tp4-1 having four β-butyloxy and two adjacent β-methoxycarbonyl chains which displays two columnar mesophase behaviours with a transition from the columnar plastic phase to hexagonal columnar phase. A significant difference between the two mesophase was observed in the variable temperature X-ray diffraction studies, and the mesophase assignment was also confirmed by polarising optical microscopy and differential scanning calorimetry. Moreover, the prepared esters in each series display the general trend of decreasing clearing temperature upon increasing alkoxy or alkoxycarbonyl chains length. The intermediate triphenylene 2,3-dicarboxylic acids were also found not only to exhibit columnar hexagonal mesophase over a narrower temperature range by maintaining high melting and clearing points but also to form organogel on mixing with toluene or dichloromethane with the assistance of hydrogen bonding.     

The influence of flexible segments on liquid crystalline properties in terms of solubility parameters. An attempt at quantitative interpretation

The phase behavior of some rodlike block molecules has been reviewed with reference to the polarity of constituent segments. It was found that the ability of the mesophase formation is connected with differences in polar character between the flexible chains and rigid cores. Thus the polar poly(oxyethylene) group connected with the polar rigid core reduces mesophase stability but is advantageous when put together with some apolar building blocks. An attempt at quantitative estimation of the incompatibilities of different parts of molecules by means of Hansen solubility parameters delta and Flory interaction parameters chi has also been made. On the basis of chi parameters the Gibbs free energies of mixing of these segments were calculated. The changes of Gibbs free energy reflecting the compatibility of segments and their tendency to the phase separation and the volume fraction of mesogenic rigid core reflecting their ability to arrangement in one direction appear to be crucial in terms of type of the mesophase formation.     

What can calorimetry tell us about changes of three-dimensional aggregate structures of phospholipids and glycolipids?

It is reported on the structural polymorphism of the main amphiphilic cell membrane compounds, phospholipids and glycolipids, with special regard to calorimetric analyses. These lipids may form a large variety of aggregate structures in dependence on their chemical primary structure, on temperature, water content, and concentrations of cations. The entity of aggregate structures is usually called the phase diagram of the respective lipids. This should, however, not to be confused with the gel and liquid crystalline phases of the hydrocarbon chains of lipids, which differ in the fluidity of the acyl chains, and between which a first order transition can be observed. Thus, in this contribution, exemplary results are presented on the structural behaviour of biologically important lipids including their phase behaviour and structural preferences under different ambient conditions, and how phase and structural transitions are connected with enthalpy changes.     

Macrophase‐separation in binary blends of symmetric polystyrene‐polybutadiene diblock copolymers

Binary blends of compositionally symmetric polystyrene‐polybutadiene diblock copolymers are investigated as a function of chain length ratio and blend composition using small‐angle neutron scattering. Three different low molar mass copolymers were blended with a high molar mass copolymer. The results are related to the theoretical phase diagram put forward by M. W. Matsen (J. Chem. Phys. 103 , 3268 (1995)). The conditions for macrophase‐separation are established, an observed asymmetry of the lamellae rich in long copolymers is discussed and the variation of the lamellar thickness with the volume fraction of short chains in the one‐phase state is compared with theoretical predictions.     

Transformation of isotactic polypropylene droplets from the mesophase into the α‐phase

The structural transformation of homogeneously nucleated metastable mesophase of polypropylene (PP) particles was investigated in this study. We demonstrated the formation of heterogeneity‐free mesophase by slow cooling of the droplets unlike mesophase formation by quenching of the PP melt, which contained large number of bulk nuclei. Submicron size PP droplets were produced by thermal break up of PP and polystyrene layered film assembly. When cooled from melt, the PP droplets crystallized into mesophase at 44 °C revealing granular morphology. Subsequent heating thermogram of the PP particles showed a broad exotherm, which was attributed to the transformation of mesophase into α‐phase. This transformation was investigated during heating by annealing the PP particles at different temperatures. Annealed PP particles were analyzed by means of thermal, morphological and structural properties measurements. Results revealed a two step process for the transformation process. In the first step, the internal rearrangement of PP chains, as against melting and recrystallization of the mesophase, was observed. Since granular morphology was not affected significantly up to 120 °C, it was suggested that translational and rotational motions of PP helices produced ordered α‐phase. In the second step, increment in grain size distribution was observed, when the droplets were annealed at 140 °C. The results were attributed to enhanced chain mobility and merging of the grain boundaries. Annealing at 160 °C revealed the formation of short lamellar structures. Crystal thickening, melting and recrystallization of α‐phase were suggested at high temperature annealing. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Ionic liquid crystals based on viologen dimers: tuning the mesomorphism by varying the conformational freedom of the ionic layer

We investigated the liquid crystal behaviour of newly synthesised bistriflimide salts of symmetric viologen dimers. A smectic A phase was observed for intermediate spacer lengths and for relatively long lateral alkyl chains. The systems were characterised by thermal analysis, polarised optical microscopy, X-ray scattering and solid-state NMR. An intermediate ordered smectic phase was also exhibited by the compounds (except for systems with very short lateral chains) consisting of molten layers of alkyl chains and partially ordered ionic layers. These results, relating to the mesomorphic behaviour of viologen salts, are qualitatively compared to those of the more common imidazolium salts, highlighting the importance of the conformational degrees of freedom of the anions and of the cationic core. It appears that fine tuning of the conformational degrees of freedom of the ionic layer is an important component of mesophase stabilisation.     

Structure and phase behavior of polyelectrolyte star solutions

Using the recently developed effective interaction potentials between polyelectrolyte stars, we examine the structure and phase behavior of solutions of the same. The effective interaction is ultrasoft and density dependent, owing to the integration of the counterionic degrees of freedom. The latter contribute extensive volume terms that must be taken into account in drawing the phase diagram of the system. The structural behavior of the uniform fluid is characterized by anomalous structure factors, akin to those found previously for solutions of uncharged star polymers. The phase diagram of the system is very rich, featuring a fluid phase at low arm numbers of the stars, two reentrant melting regions, as well as a variety of crystal structures with unusual symmetry. The physical origin of these features can be traced back to the ultrasoft nature of the effective interaction potential.