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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. 相似文献
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液晶聚合物从结构上可分为3种:侧链型、主链型和主侧链型。侧链型液晶聚合物主要是聚丙烯酸酯类、聚硅氧烷类以及磷腈聚合物类。Gray等对聚丙烯酸酯类含不同取代基的联苯结构液晶聚合物进行了研究,结果表明无间隔基且取代基为氰基和饱和脂肪基时,该聚合物呈现近晶型液晶行为。为了增加介晶单元的长径比及刚性,本文在聚甲基丙烯酸酯侧链 相似文献
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利用紫外-可见光谱,对比研究了尾挂侧链液晶聚合物和腰挂侧链液晶聚合物在结晶相和液晶相转变过程中的液晶基元取向情况.研究表明,石英基材表面倾向于诱导偶氮液晶基元垂直于基材排列;观察到了在液晶态尾挂侧链液晶聚合物和腰挂侧链液晶聚合物的不同取向行为.在室温下重新结晶数天后,腰挂液晶聚合物的紫外可见光谱缓慢回复. 相似文献
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基于聚烯烃用成核剂的结构特征设计合成了两种极性基团和非极性基团交替排列的乙烯基单体,并利用自由基引发聚合,制备出相应的侧链型液晶聚合物.采用元素分析、红外光谱和核磁共振氢谱对所合成单体和聚合物的结构进行了确认.并采用热失重(TGA)和差示扫描量热仪(DSC)研究了聚合物的热稳定性和相转变温度.结果表明,所合成聚合物的起始热分解温度均在337℃以上,具有优异的热稳定性;液晶相变温度区间可达186 K,具有较宽的液晶态温度范围.热台偏光显微镜(HS-POM)研究结果表明,聚合物均呈现出纹影织构,证明所合成的聚合物均为热致向列型侧链液晶高分子.采用DSC和HS-POM研究了所合成的侧链液晶聚合物对高密度聚乙烯(HDPE)异相成核结晶行为的影响.结果表明,侧链型液晶聚合物在提高HDPE结晶温度、结晶度以及降低HDPE晶粒的尺寸及分布方面均有优异的效果,是一类HDPE有效的成核剂. 相似文献
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液晶弹性体是交联型液晶大分子,兼具液晶取向有序性和交联聚合物熵弹性等特性,在传感器、触发器、微流体装置和仿生器件等方面具有很好的应用前景.制备液晶弹性体的微结构,探索其独特的刺激响应性,是目前液晶弹性体研究的重要方向.侧链液晶弹性体的液晶相态类型取决于其液晶基元和主链的连接方式.腰接型侧链液晶弹性体倾向于形成向列型液晶相,具有较快的响应速度和形变程度,是一类独特的液晶弹性体.本文重点介绍腰接型液晶弹性体微结构(如微米柱、微米线等)的制备;利用金纳米粒子的光热转换效应,实现液晶弹性体光响应性的新途径;以及腰接型侧链液晶弹性体仿生微结构的功能性等.同时还对该领域的发展前景进行了展望. 相似文献
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<正>《高分子学报》于2017年先后出版了超分子聚合物专辑、庆祝颜德岳院士80华诞专辑、庆祝《高分子学报》创刊60周年专辑,以及钱人元先生诞辰100周年纪念专辑,迎来了回顾历史和展望未来的发展新阶段.本期是为纪念甲壳型液晶高分子30周年而出版的专辑.传统的液晶高分子有主链型和侧链型之分.前者的液晶基元在高分子主链 相似文献
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聚硅氧烷侧链液晶高分子的合成与表征 总被引:6,自引:0,他引:6
研究以对-烯丙氧基苯甲酸对-氰基苯酚酯为单体的聚硅氧烷侧链液晶高分子的合成方法。首先利用Williamson反应生成醚、羧酸酰化、酯化反应得到单体,然后利用硅氢化反应将单体接枝到聚甲基氢硅氧烷上得到目标产物。用IR,NMR及热台偏光显微镜等方法对单体和聚合物进行了结构表征和液晶行为分析。优化了对-烯丙氧基苯甲酸对-氰基苯酯为单体的聚硅氧烷侧链液晶高分子的合成工艺条件,提高了产率。样品表征结果证明单体和聚合物均呈现近晶液晶相,为特殊功能材料提供了原料。 相似文献
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R. Kh. Freidlina V. I. Dostovalova N. A. Kuz'mina E. C. Chukovskaya 《Magnetic resonance in chemistry : MRC》1981,15(2):133-138
Carbon-13 NMR spectra of mono- and disubstituted aromatic compounds including DDT, its analogues, homologues, derivatives and certain model compounds have been studied. The Savitsky scheme of carbon chemical shifts in disubstituted benzenes is applicable to these compounds. The data obtained show that in mono- and disubstituted aromatic compounds containing two different substituents in the α- and β-positions of the side chain, the substituted ring carbon atom shifts follow the additivity rule and can be calculated from substituent increments. Mutual effects of substituents in the ring and in the side chains are analysed. The chlorine atoms in α-position to the phenyl ring give rise to an additive α-effect of about 25 ppm, as in perchloroalkanes. The influence of a β-chlorine atom in the side chain on the substituted carbon atom in the ring is, however, only 3 ppm as against the usual value of about 10 ppm for the β-effect in alkyl chains. Moreover, the first β-chlorine substituent has no noticeable influence on the substituted ring carbon chemical shift: the effect of 3 ppm is transferred to the para-carbon atom almost without attenuation. The ring substituted carbon atom signal shifts caused by the γ-effect of chlorine in the side chain are similar to those observed in aliphatic chains. The ortho-chlorine substituents shift the side chain α-carbon atom signal by 3.6-5.2 ppm to high field compared to para-chlorophenyl compounds. This is similar to the chlorine γ-effect in aliphatic chains. 相似文献
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The syntheses of new liquid crystalline compounds containing β-hydroxy-, β-chloroketone and α,β-unsaturated ketone moieties are described. The key intermediate 1-(4-hydroxyphenyl)-3-hydroxyoctan-1-one was obtained by the hydrogenolysis of the heterocycle in 3-(4-hydroxyphenyl)-5-pentyl-2-isoxazoline. Dehydratation of the intermediate β-hydroxyketone led to 1-(4-hydroxyphenyl)-oct-2-en-1-one. Reaction of 1-(4-hydroxyphenyl)-3-hydroxyoctan-1-one with hydrochloric acid yielded 1-(4-hydroxyphenyl)-3-chlorooctan-1-one. The target liquid crystalline compounds were synthesized by the esterification of these phenols with corresponding acids. The relationships between the moiety type in the terminal chain and the liquid crystalline properties are discussed. 相似文献
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Wei Zhou Ruonong Fu Rongji Dai Zaifu Huang Yanfei Chen 《Journal of separation science》1994,17(10):719-722
A new kind of side chain liquid crystalline polysiloxane containing a crown ether with a longer spacer (PSC-11) has been prepared and coated on a fused silica capillary column. The main chroma-tographic characteristics including efficiency, polarity, and selectivity have been examined. The phase exhibits the retention properties of both liquid crystal and crown ether stationary phases and possesses higher efficiency and better selectivity than PSC-3, which has a shorter spacer between the main polysiloxane chain and liquid crystalline side chain. 相似文献
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Isao Ando Yige Yin Chenhua Zhao Sho Kanesaka Shigeki Kuroki 《Macromolecular Symposia》2005,220(1):61-74
In this lecture the measurements and analyses of the isotropic and anisotropic diffusion coefficients(D) of rod-like polypeptide such as poly(γ-L-glutamate)(PLG) with n-alkyl side chains, of which the main chain takes the α-helical conformation, as a function of the main chain length in the thermotropic and lyotropic liquid crystalline phases over a wide range of temperatures from 30 to 80°C by means of pulse high field-gradient spin echo 1H NMR method have been introduced. In the anisotropic diffusion, the D∥ value in direction parallel to the α-helical chain axis is found to be much larger than the D⊥ value in direction perpendicular to the α-helical chain axis. The diffusion process is followed by the Kirkwood theory. Further, it is described that the diffusion in the nematic liquid crystalline phase is much slower than that in the isotropic phase. 相似文献
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Depending on the nature of the halogen, α-fluoro- and α-chloro-α,β-unsaturated carbonyl compounds (whose reduction potentials are greater than ? 2.4V) react in different ways with lithium dimethylcuprate. With α-fluoro derivatives, both 1,2- and 1,4-addition is observed, their ratios depend on the steric hindrance of the β-position. 1,4-Addition products are obtained from aldehydes and β-monosubstituted α-chloro-α,β-ethylenic ketones and esters. β,β-Disubstituted α-chloro ketones and esters give only reduction of halogen via halogen-metal exchange. 相似文献
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The orientational order of a liquid crystalline side chain polysiloxane has been investigated by means of polarized light spectroscopy and dielectric relaxation measurements. The order parameters (P2) and (P4) have been determined as a function of the temperature for the smectic and nematic phases. The orienting properties of the polysiloxane investigated have been compared with those of a polysiloxane with the same mesogenic groups, but a shorter spacer. 相似文献
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Masanori Matsui Yuji Yamane Hideaki Kimura Shigeki Kuroki Isao Ando Kai Fu Junji Watanabe 《Journal of Molecular Structure》2003,650(1-3):175-180
Solid state 13C NMR experiments on poly(p-biphenylene terephthalate) with long n-dodecyl side chains have been carried out over a wide range of temperatures, in order to elucidate conformational and dynamical behavior of the polyester in the crystalline state and thermotropic liquid crystalline state. From these experimental results, it is found that at temperatures from room temperature to 80 °C the n-alkyl side chains take both of the immobile and the mobile regions, and at temperatures above 120 °C take only the mobile region. In the immobile region the n-alkyl side chains are in the all-trans zigzag conformation and in the mobile state are undergoing fast exchange between the trans and gauche conformations. On the other hand, the terephthalate moiety of the main chain undergoes rotational motion after the melt of n-alkyl side chains as the temperature is increased. 相似文献