Structure and dynamics of rodlike polyester with long n-alkyl side chains over a wide range of temperatures by solid state C NMR

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.     

SYNTHESIS AND CHARACTERIZATION OF PALLADIUM COORDINATING IMINE SIDE CHAIN LIQUID CRYSTALLINE POLYSILOXANES

New thermotropic chloro-bridged dinuclear palladium coordinating imine side chain liquid crystalline polysiloxanes have been synthesized. Their mesomorphic properties have been investigated by DSC, X-ray diffraction and polarizing microscopy. The polymeric complexes show nematicdiscotic (Nd) mesophase. It is found that the temperature range of liquid crystalline state of chloro- bridged polymeric complexes is much wider than that of acetato- bridged ones and imine side chain polysiloxane. This indicates that the disc-like chloro-bridged palladium complexing units play a role as mesogen in mesophase.     

含液晶基元的缩聚单体及其序列嵌段共聚物的合成

本文介绍了含液晶基元的缩聚单体的合成,2-甲基-1,4-苯撑双(4-氯甲酰)苯甲酸酯,以及由此单体与1,10-癸二醇、聚环氧丙烷二醇合成的含液晶性及非液晶性两种序列结构的嵌段共聚物。聚合物的液晶态性质由偏光显微镜和DSC进行初步表征。在研完中观察到:在对数比浓粘度较大的样品的DSC图中、在熔点之后存在一显著放热峰。这种异常现象可能意味着液晶态分子的另外一种分子运动。     

SYNTHESIS AND PROPERTIES OF METAL COMPLEXES OF β-DIKETONE BASED SIDE CHAIN LIQUID CRYSTAL POLYSILOXANE

A new type of metal coordinated liquid crystalline polymers has been synthesized by complexation of metal ions with β-diketone based side chain liquid crystal polysiloxane (DKLCP). The complexation of copper ions with DKLCP greatly increases the phase transition temperature T_k from crystalline state to liquid crystalline state and T_(cl) from LC to isotropic state and makes the range of phase transition ΔT (ΔT=T_(cl)-T_k) widened. These complexes are soluble in common organic solvents. However, the incorporation of europium ions into DKLCP molecules gives rise to reduction in liquid crystallinity and crosslinking in some cases. The DKLCP coordinated with suitable amount of Eu ions can show good liquid crystallinity and fluorescent property.     

含X-型二维液晶基元和反式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6冠醚环的液晶共聚酯的合成与表征

以4,4-′(α,ω己二酰氧)二苯甲酰氯(M1)、2,5-二(对辛氧基苯甲酰氧基)氢醌(M2)和反式4,4′-双(4羟基苯基偶氮)二苯并18冠6(M3)为单体,通过溶液共缩聚反应,合成了一系列含X型二维液晶基元和反式4,4′双(4羟基苯基偶氮)二苯并18冠6冠醚环的主链型液晶共聚酯.共聚酯的分子量不高,[η]在0.37～0.25dL g之间.单体的化学结构通过IR、UV、H NMR、MS和元素分析等方法确证.共聚酯的外观为黄色粉状固体,除CP9外,室温下不溶于CHCl3和THF溶剂.共聚酯的性质采用GPC、[η]、DSC、TG、WAXD和POM等方法进行了研究.发现所有的共聚酯加热到各自的熔融温度以上都能形成液晶态,在液晶态可以观察到近晶相的镶嵌织构或焦锥织构或破扇型织构和向列相的球粒织构或丝状织构或纹影织构.共聚酯的熔融温度(Tm)和各向同性温度(Ti)随共聚酯分子中反式4,4′双(4-羟基苯基偶氮)二苯并18冠6用量的改变呈规律性变化.WAXD研究进一步证实了共聚酯的液晶性.     

聚乙烯基吡啶共聚物与取代苯基偶氮苯酚复合物的制备及其液晶性质

通过分子间弱相互作用力组装形成的液晶高分子与一般侧链液晶高分子相比，其介晶基元与聚合物主链搭配选择范围宽，且易于组装制备．因此，将氢键［１，２］，离子键［３，４］等引入液晶高分子制备领域，越来越引起人们的兴趣．目前以吡啶 羧基氢键组装成的侧链液晶高分...     

PEO/LiClO_4复合体系电解质膜的固体NMR研究

自1973年,Wright[1]等发现聚氧乙烯(PEO)/碱金属盐复合物具有离子导电性之后,人们对复合物的导电机理以及如何进一步提高复合物导电率等问题开展了大量研究.长期以来,人们普遍认为复合物中碱金属离子的传输是通过PEO非晶区的链段运动来实现的[2],因此探索新的物理或化学方法,通     

聚苯撑苯并二噻唑的甲基磺酸溶液的相转变过程及其动力学研究

用退偏振光强度法及偏光显微镜研究了溶致性液晶高分子聚苯撑苯并二噻唑的甲基磺酸溶液(PBT/MSA)由液晶相至各向同性相(N→I转变),及由各向同性相至液晶相(I→N转变)的相变过程.液晶相的形成(I→N)服从Av-rami方程,Avrami指数为1左右,表明该体系的液晶相是以一维棒状方式形成的.相转变温度与浓度有关,提高温度可加速在应力下液晶相长程有序结构的形成.     

Thermotropic liquid crystalline polymers. I. Cholesterol-containing polymers and copolymers

An approach to the creation of thermotropic cholesterol-containing liquid crystalline polymers by the chemical binding of cholesterol molecules with side chains of comblike polymers is presented. This type of structure permits a decrease in the steric hindrances provided by the backbone chains for the purpose of realizing the liquid crystalline state. A number of new cholesteric esters of poly(N-methacryloyl-ω-aminocarbonic acid)s (PChMAA-n) with different side-chain lengths (n = 2–11) as well as a series of copolymers of ChMA-n with n-alkylacrylates and n-alkylmethacrylates have been synthesized. The experimental evidence of liquid crystalline structure formation in these polymers in glass, viscoelastic, and fluid states is discussed. Molecular and supermolecular structures of cholesterol-containing comblike polymers have been studied and the model of macromolecular packing in the liquid crystalline state is proposed. It is shown that the existence of a layered order of side methylene groups together with ordering of cholesterol groups is necessary to the production of the liquid crystalline state in these polymers.     

聚苯撑苯并二噻唑的甲基磺酸溶液的相转变过程及其动力学研究

 用退偏振光强度法及偏光显微镜研究了溶致性液晶高分子聚苯撑苯并二噻唑的甲基磺酸溶液(PBT/MSA)由液晶相至各向同性相(N→I转变),及由各向同性相至液晶相(I→N转变)的相变过程.液晶相的形成(I→N)服从Av-rami方程,Avrami指数为1左右,表明该体系的液晶相是以一维棒状方式形成的.相转变温度与浓度有关,提高温度可加速在应力下液晶相长程有序结构的形成.     

长链脂肪酸魔芋葡甘聚糖酯的制备及乳化性能研究

采用非均相酰化法制备了四个系列的长链脂肪酸魔芋葡甘聚糖酯（ＫＧＭＥ）．ＤＴＡ图显示了葡甘聚糖酯的晶态结构变化,Ｘ 射线衍射分析表明了不同长度的酰链对葡甘聚糖酯晶态结构的影响．初步研究了葡甘聚糖酯在芳香烃及环烷烃两种水包油（Ｏ／Ｗ）乳液体系中其取代度与乳化力的关系．实验证明在水包油乳液体系中,取代度在某一范围的葡甘聚糖酯显示出较好的乳化能力,且在高盐浓度和酸性情况下,仍给出好的乳化作用．丁香油 水（Ｏ／Ｗ）乳液体系在室温下静置四个星期未发现破乳分离现象     

固态高聚物状态方程的研究

本文从理论上导出了一个新的三参数固态高聚物的状态方程:P=(B_0/4.98)[((V_0/V))~(7.14)-((V_0/V))~(2.16)+(T/T_0)]在不发生转变的情况下,它适用于描述固态高聚物的压强—体积—温度关系,方程形式简单,参数物理意义明确.     

聚丙烯酸酯型高分子侧链液晶的合成及其对聚乙烯成核结晶行为的影响

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.     

Synthesis and X-ray structural studies of pyrimidin-2,4-dione and 2-thioxo-1H-pyrimidin-4-one bearing chloroethyl moiety

The present work is aimed to investigate non-covalent bonding capabilities of uracil derivative bearing hydrophobic side chain in solid crystalline state. The synthesis and crystal structure of 5-(2-chloro-ethyl)-6-methyl-uracil 3 and 5-(2-chloro-ethyl)-6-methyl-2-thiouracil 4 are described, which revealed sulfur-π interaction including resonance-induced intermolecular H-bonding in 4 whereas compound 3 showed only strong H-bonding and formed a dimer. Thus the analysis of such moieties in solid state provides useful structural information on the binding characteristics of functional groups and has implications for the de novo design of drugs and enzyme's inhibitors.     

Side‐chain crystallization behavior of graft copolymers consisting of amorphous main chain and crystalline side chains: Poly(methyl methacrylate)‐graft‐poly(ethylene glycol) and poly(methyl acrylate)‐graft‐poly(ethylene glycol)

Graft copolymers consisting of amorphous main chain, poly(methyl methacrylate) (PMMA), or poly(methyl acrylate) (PMAc), and crystalline side chains, poly(ethylene glycol) (PEG), have been prepared by copolymerization of PEG macromonomers with methyl methacrylate or methyl acrylate (MMAx or MACx, respectively). Because of the compatibility of PMMA/PEG and PMAc/PEG, from small‐angle X‐ray scattering results, the main and side chains in graft copolymers were suggested to be homogeneous in the molten state. Differential scanning calorimetry (DSC) cooling scans revealed that PEG side chains for graft copolymers with large PEG fractions were crystallized when the sample was cooled, with a cooling rate of 10 °C/min. The spherulite pattern observed by a polarized optical microscope suggested the growth of PEG crystalline lamellae. Crystallization of PEG in MMAx was more restrained than in MACx. From these results, we have concluded that the crystallization behavior of the grafted side chains is strongly influenced by the glass transition of a homogeneously molten sample as well as dilution of the crystallizable chains. Domain spacings for isothermally crystallized graft copolymers were described by interdigitating chain packing in crystalline–amorphous lamellar structure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 79–86, 2005     

Synthesis and mesomorphic properties of Cu-coordinating liquid crystalline polysilsesquioxanes with heptyl side groups

In order to study the influence of the concentration of a flexible group on the liquid crystal behaviour of copper-containing complexes, series of Cu-coordinated, beta-diketone-based liquid crystalline polysilsesquioxanes (abbr. H-DK-Cu) and random copolymethylsilsesquioxanes (abbr. Me-DK-Cu), have been synthesized by the hydrosilylation reaction of a vinyl-terminated beta-diketone and 1-heptene with the polyhydrosilsesquioxane (H-T) and with the random copolymethylhydrosilsesquioxane (Me-T), followed by reaction with Cu(NH₃)₄Cl₂. Their mesomorphic properties were investigated by differential scanning calorimetry and optical polarizing microscopy. The H-DK-Cu and Me-DK-Cu complexes with M_w of approximately 1 x 10⁴ are thermotropic liquid crystalline polymers and their clearing temperature and mesophase ranges are lower than those of the corresponding Cu-coordinated, beta-diketone-based liquid crystalline polymethylsilsesquioxanes (Cu-FBDKLCP) without the n-heptyl flexible group. However, their liquidity within the temperature range of the liquid crystal state is better. The results are mainly attributed to the heptyl, flexible side group.     

聚己内酯在有机/无机杂化体系中的受限结晶行为

通过Sol Gel技术合成了聚己内酯 (PCL) /二氧化硅 (SiO2 )杂化材料 ,并对杂化样品进行了DSC和WAXD测试 .实验结果表明杂化样品中PCL的结晶度随二氧化硅含量增加而减小 ,当样品中二氧化硅含量达到 60 %时 ,PCL为非晶态 ;含有PCL结晶的杂化样品中PCL熔融温度基本相同 ,但是比纯PCL的熔融温度低 .杂化样品中结晶PCL的结晶结构和微晶尺寸和纯PCL的一致 .这说明杂化材料中PCL的结晶行为和结晶度受到了限制 ,含PCL结晶的样品中PCL的结晶结构和微晶尺寸并没有受到影响 .     

Crystalline Cooperativity of Donor and Acceptor Segments in Double‐Cable Conjugated Polymers toward Efficient Single‐Component Organic Solar Cells

The crystalline cooperativity of the donor and acceptor segment in double‐cable conjugated polymers plays an important role in the nanophase separation and photovoltaic performance in single‐component organic solar cells (SCOSCs). Two double‐cable conjugated polymers with the same conjugated backbone and perylene bisimide (PBI) side units were designed in which PBIs were positioned symmetrically and perpendicularly ( P1 ) and asymmetrically and slantingly ( P2 ) along the conjugated backbones. After thermal annealing, both conjugated backbones and PBI side units in P1 tend to form ordered nanostructures, while PBI side units in P2 dominated the crystallization and hamper the crystallization of conjugated backbones. P1 showed good crystalline cooperativity between conjugated backbones and PBI side units, resulting in improved power conversion efficiencies (PCEs) up to 3.43 % in SCOSCs, while P2 with poor crystalline cooperativity exhibited PCEs below 2.42 %.     

聚苯醚/聚苯乙烯共混物溶液浇铸膜的热演化行为

聚苯醚与聚苯乙烯共混物是目前相容性最好的共混体系之一。几十年来人们对该共混体系相容的原因进行了广泛的研究^[1-4]。聚苯醚是半结晶聚合物,在溶剂或溶剂蒸气存在的条件下容易形成结晶,溶剂的性质及结晶的条件都会影响聚苯醚的结晶结构及其形态^[5-8]。用溶液共昆、凝聚成膜的方法制备共混物时,一种结晶性高分子怎样与另一种高分子演化成相容的非晶共混体系,是一个比较有意义的研究课题。本文运用DSC方法,研究了聚苯醚与聚苯乙烯两者溶液共混凝聚成膜后,在各种热历史条件下结晶结构的消亡和演化成非晶相容体系的行为。     

成膜溶剂对聚4-甲基戊烯-1膜的形态结构和透过行为的影响——Ⅰ.膜的结晶性质与表面形态

以聚4-甲基戊烯-1(PMP)为膜材质,分别以环己烷、三氯乙烯、四氯乙烯、环己烷/三氯乙烯及环己烷/四氯乙烯为溶剂,研究了这些溶液浇铸膜的结晶性质和表面形态。结果表明,溶剂对PMP的相对溶解能力和挥发速度同所成膜内PMP的结晶形式和结晶度密切相关;不同溶剂体系的PMP溶液浇铸膜的表面形态也不尽相同。并发现以四氯乙烯(或三氯乙烯)为溶剂或溶剂组分之一的PMP溶液浇铸膜存在未见报道的Ⅵ型结晶。