片晶装饰技术研究高分子液晶向列相的向错

采用片晶装饰技术和四氧化钉染色技术相结合在透射电镜下研究了热致性高分子液晶的向错结构，在一种热致性聚芳酯的冻结液晶态中观察到了向错强度分别为Ｓ＝±１／２和Ｓ＝±１的两类共六种的向错形态，以及每个向错与其相邻向错之间相互联结和相互作用的状态．     

SYNTHESIS AND PROPERTIES OF NEW MESOGEN-JACKETED LIQUID CRYSTALLINE POLYMERS*

Some new mesogen-jacketed liquid crystalline polymers (MJLCP) with polymer backbones, spacers, andmesogenic units of different structures were synthesized by radical polymerization. The mesomorphic behavior of thesepolymers was examined using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Theirliquid crystallinity is influenced by the variation of polymer backbone, spacer, mesogenic unit and its terminal groups. Theresults show that 1) a more flexible polymer main-chain is more favorable to the formation of a liquid crystal phase, while 2)a flexible spacer will decrease the "Jacket Effect" and the liquid crystallinity and 3) a subtle modification of the terminalgroups on the mesogenic unit may also have a significant influence on properties of the polymers.     

THE SPHERULITE-LIKE STRUCTURE OF MAIN CHAIN THERMOTROPIC AROMATIC COPOLYESTERS

A new spherulite-like structure of main chain thermotropic aromatic copolyesters formed insolution cast specimens was observed and was studied by means of polarizing microscopy, X-ray diffraction,SEM and IR spectrometry. Results indicate that the spherulite-like structure of main chain thermotropicaromatic copolyesters formed from the casting solution (phenol/Cl_2CH_2CH_2Cl_2) is not a real crystal but only ahigh oriented arrangement of the macromolecular chains as a spherulite. This resulted from the interactionbetween the needle-like crystal of phenol and the rigid mesomorphic groups of molecular chain. The parallelpacking of extended copolyester molecules along the needle-like crystal of phenol leads to the formation ofthe spherulite-like structure.     

SYNTHESIS AND CHARACTERIZATION OF SOME THERMOTROPIC LIQUID CRYSTALLINE POLYAMIDES

A series of novel mesogenic polyamides containing a flexible pendent side group wassynthesized by solution condensation polymerization. The new monomers, diacids and di-amines containing flexible elements of diferent lengths, were also synthesized and character-ized by ~1HNMR, mass spectroscopy and elemental analysis. The polymers were character-ized by viscosity measurements, differential scanning calorimetry (DSC), X-ray diffiactionand polarizing optical microscopy These studies revealed that polyamides containingflexible elements of a sufficient length exhibited thermotropic liquid crystalline(LC) pro-perties. The melting temperatures of this series of polymers were particularly sensitive tothe length of the flexible segment on the main chain and that of the flexible pendent esterside chain. Lyotropic LC behaviours were also observed in solution.     

NUCLEATION ACTION OF THERMOTROPIC LIQUID CRYSTAL POLYMERS IN THE BLENDS WITH PET

The present work concerns the crystallization of PET accelerated by addition of thermotropic liquid crystalline polymers (TLCP)based on two aromatic copolyesters: PHB/PET (60:40 ) and PHB/HDA/2,6-DNA /IPA ( 50:25 : 12.5 : 12.5 ). The investigation has been made by measurements of the cold-crystallization and melt-crystallization temperatures by DSC and of the changes of density and depolarizing light intensity during the isothermal process. In addition, the morphology of selectively etched surface of compressing pellets proved the presence of crystalline fibrillar structure, it can be supposed to have grown up from the micelle nucleus based on bundle of rigid TLCP chains.     

CRYSTALLIZATION BEHAVIOR OF A THERMOTROPIC LIQUID CRYSTAL COPOLYESTER

A thermotropic liquid crystal copolyester resin based on p-hydroxybenzoic acid, 2, 6-naphthoic acid, hydroxyquinone and PET was synthesized by melt condensation and studied. The results based on DSC and X-ray diffraction indicated that there were a rapid and a slow crystallization processes for the copolyester at certain conditions. A critical temperature was suggested, below which the slow crystallization could hardly happen. Above the critical temperature the extent of the slow crystallization process depended not only on annealing temperature but also on the annealing time. A fine crystal structure with high melting point and narrow diffraction peak was formed under favorable conditions.     

MELT BLENDS OF POLY (BUTYLEN TEREPHTHALATE) AND A THERMOTROPIC LIQUID CRYSTALLINE POLYMER

With the help of differential scanning calorimetry, cone-plate and capillary rheometry andscanning electron microscopy, a research has been conducted on rheological behavior,crystallization and morphology of poly (butylene terephthalate) (PBT) blends containing athermotropic LCP. The blend has zero entrance pressure loss, although the LCP has rather largeone. The viscosity curve of the blend lies between those of the LCP and PBT. The crystallizationof PBT is not affected by the presence of the LCP together with no indication oftransesterification between the two ingredients. LCP spheres and ellipsoids with the size of 0. 5--1. 5 μm disperse in PBT matrix uniformly, which is related to the viscosity ratio of the twocomponents.     

CHOLESTERIC LIQUID CRYSTALLINE CHARACTER ON THE SURFACE OF CHITOSAN/POLYACRYLIC ACID COMPOSITES*

The cholesteric liquid crystalline structure in chitosan/polyacrylic acid composite films was studied by surfacetechniques. A periodical lamellar-like structure was observed in the permanganic acid etched film sufface by both scanningelectron microscopy (SEM) and atomic force microscopy (AFM), instead of the thumb-print texture which can be detectedwith polarized optical microscopy. It is suggested that the periodical lamellar-like structure is induced by the etchingselectivity between cholesteric layers due to different molecular arrangement on the film surface. Four kinds of perpendiculardisclinations, i.e. χ→τ→λ~+, χ→λ+τ~+, χ→τ+τ~+ and χ→λ~- +λ~+, were found in the composite films from SEMobservations. The smallest periodicity of lamellar-like structure (equals to half pitch) is 20～40 nm measured with AFM.     

EFFECT OF SEQUENCE STRUCTURE ON THE THERMOTROPIC LIQUID CRYSTALLINE PROPERTIES OF POLYESTERAMIDES BASED ON DIMETHYLBENZIDINE, BISPHENOL-A AND ρ-TEREPHTHALYL CHLORIDE*

A series of thermotropic liquid crystalline polyesteramides with differ-ent sequence structure based on dimethylbenzidine (DMBD), bisphenol-A(BPA) and p-terephthalyl chloride (TPC) was synthesized by changing the feeding order of monomers inlow temperature solution polycondensation system. By means of NMR and a computer pro-gram the sequence structure parameters were measured. The effect of sequence structureon liquid crystalline phase transition temperature of PEAs obtained was investigated.     

含热致液晶性共聚酯的聚砜共混物

将一种含萘环的热致液晶性共聚酯与聚砜材脂熔融共混并挤塑成条．毛细管流变性测试表明，这一共聚酯降低了共混物的表观粘度，甚至低于其本身的粘度．共混物受剪切作用形成了各向异性的微纤增强结构，并具有皮芯结构．在液晶聚合物含量低到２％与０．５％的样条中仍有共聚酯微纤形成．共聚酯微纤提高了聚砜的力学性能，含２０％共聚酯共混物挤塑条的位伸模量为聚砜树脂的二倍半．     

MORPHOLOGICAL STUDIES OF A THERMOTROPIC SIDE-CHAIN LIQUID CRYSTALLINE POLYMER DURING MESOPHASE TRANSITIONS*

The morphological features of a side-chain liquid crystalline polymer during the mesophasetransitions were investigated by using the DSC technique. The polymer used was polyacrylate with mesogensof three benzene rings attached to the main chain through a flexible spacer. A special two-phase texture wasobserved in the transition temperature range. Similar to main-chain liquid crystalline polymers the transitionprocess of the side-chain liquid crystalline polymer was composed of an initiation of the new phase at localplaces of the old phase matrix and a growth process of the new phase domains.     

THERMAL ANALYSIS AND STRUCTURE STUDIES ON THE BLENDS OF LIQUID CRYSTALLINE COPOLYESTERS AND PET, PBT

The apparent uniform blends of liquid crystalline aromatic copolyesters and semiflexible polyesters PET or PBT were obtained by mechanical mixing in the molten state within certain range of composition.The effects of blending with liquid crystalline components on the structure of homopolyester matrix were examined by thermal analysis and X-ray diffraction. These results suggest that the LC component in the blend may possibly be acting as a nucleating agent, or it may induce axial orientation of molecules promoting the local ordering of matrix. For the blends of PET, these influences mainly display in narrowing the width of cold crystalline peak and enhancing the main peak of x-ray diffraction; and for the blends of PBT, the pre-melting crystalline peak was enhanced.     

CRYSTALLINE MORPHOLOGY IN A SERIES OF CH3-SUBSTITUTED THERMOTROPIC AROMATIC POLYESTERS WITH EVEN AND ODD FLEXIBLE SPACERS*

 Crystalline morphology in a series of CH₃-substituted main chain thermotropic aromatic polyesters with even and odd numbered methylene spacers has been studied by polarizing optical microscopy (POM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). On crystallization from solution evaporation spherulites of radial structure were observed in the polymers with even numbered spacers, but spherulites with concentric rings form in the polymer with odd numbered spacers. Both spherulites have a lamellar structure, which is about 10 nm in thickness. On crystallization from nematic glassy state spherulites can not be grown; lamellar structure was only observed around disclinations in a specimen during crystallization. In the case of crystallization from nematic melt two types of spherulites can be observed for the sample with even numbered spacers. For the sample with odd numbered spacers spherulites can not be formed, but only irregular crystallites.     

热致液晶共聚酯对聚丙烯结晶的诱导作用

用差示扫描量热法和光学解偏振法研究了热致液晶性芳香共聚酯与聚丙烯共混物的等温和非多温结晶行为.结果表明,这一热致液晶聚合物对聚丙烯结晶有诱导成核和加速作用.当共聚酯含量在2-5％之间时,聚丙烯的结晶速率最快.偏光显微镜的观察揭示出在聚丙烯熔体中原位形成的液晶聚合物微纤诱导了聚丙烯横穿晶的形成.     

一类可纺丝的全芳香热致性液晶共聚酯的合成和表征

利用Higashi芳香聚酯直接缩聚法的原理 ,采用一步混合投料直接缩聚的方法 ,以对羟基苯甲酸(PHB)、间苯二甲酸 (MPA)、4 ,4′ 二羟基二苯酮 (DHBP)和对苯二酚 (HQ)为单体原料 ,合成了全芳香共聚酯 .该合成方法反应条件温和 ,简单易控 ,产物分子量高 .用差热分析 (DSC)、热重分析 (TA)、偏光显微镜 (PLM)、广角X 射线衍射 (WAXD)等测试分析手段对共聚酯的热性能和液晶特性进行了表征 .研究结果表明 ,利用此方法合成所得的聚合物呈明显的向列型热致液晶特性 ,热稳定性高 ,并具有极易成纤的特点 ,有望成为一种可用于纺丝的全芳香热致液晶共聚酯材料     

STUDIES ON CRITICAL CONCENTRATION OF LIQUID CRYSTALLINE ETHYLCELLULOSE

Critical concentrations of lyotropic liquid crystalline ethylcellulose in more than tensolvents were determined using both Abbe refractometer and polarized microscopy. Criti-cal concentration C_(crit) of forming liquid crystal phase decreased with increasing solubilityparameter δ of solvent until approaching the δ of polymer. Although the alcohols usedas solvents had the same variation rule, the critical concentration values of their solutionswere much higher, due to their excessive large hydrogen bond component of δ. The experi-ments of using mixed solvents which showed good linear relation between C_(crit) and δ alsoproved this rule. A technique of Transmission Optical Analysis was first used to estimatethe concentration dependence of critical phase transition temperature T_(crit) of EC, and aT-C phase diagram could be drawn.     

一种新型聚酯醚砜热致液晶高分子的合成与表征

由对苯二甲酸、４，４＇－双（４－羟基苯氧基）二苯枫和对羟基苯甲酸合成了具有液晶特性的一种新型聚酯醚砜．从反应介质预聚合和后聚合等因素讨论了提高聚合物粘度的途径，以ＤＳＣ、偏光显微镜和Ｘ－线衍射仪等方法表征了其液晶特性．     

SYNTHESIS OF LIQUID CRYSTALLINE POLYACRYLATES WITH THIOESTER AS BRIDGE-BOND

A new series of acrylates with the same mesogens containing thioester as bridge-bondwere synthesized, and the acrylates were characterized by H~1 NMR, IR and MS. Thepolymers were obtained by radical polymerization using AIBN as initiator. The monomersand polymers exhibit thermotropic-enantiotropic liquid crystalline behavior.     

STUDIES ON THE SEQUENCE STRUCTURE OF TPA/EG/PHB LIQUID CRYSTALLINE COPOLYESTERS

In this paper, the sequence structure of TPA/EG/PHB liquid crystalline copolyesters made from different synthetic methods has been studied by ~1H-NMR with the help of computer program of processing peaks. The results showed that the ether bonds were not observed in TPA./EG/PHB copolyesters and the synthetic process had a great effect on their sequence structure. Under certain conditions, the high,random TPA/EG/PHB copolyesters which were considered to have higher performances than PET/xPHB could be obtained.     

PRIMARY STUDY ON BLENDS BASED ON THERMOTROPIC LIQUID CRYSTAL COPOLYESTER AND PET

The blend system composed of PET and thermotropic liquid crystal copolyester based on hydroxy benzoic acid, terephthalic acid, diacetylnaphthalene and PET was studied. The results indicated that LCP could play the role of crystal nuclei. The introduction of LCP decreased the melt viscosity of the system and fibrillous structure could be formed in favor conditions.