LAMELLAR STRUCTURE OF THERMOTROPIC LIQUID CRYSTALLINE POLYMERS

The lamellar structure of a thermotropic aromatic polyester with flexible spacer has beenstudied by using transmission electron microscopy. It was found that the lamellar structure couldbe observed in the crystalline samples of this semirigid polymer crystallized from different states.The thickness of lamellae is around 10 nm, which is similar to that of the conventional polymersof flexible chain molecules. The molecular chains in the lamellae are oriented in the thicknessdirection as determined by electron diffraction. The possibility of molecular chains folding in the lamellae has been discussed.     

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.     

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.     

SYNTHESIS AND PHASE BEHAVIOUR OF CHIRAL COMBINED MAIN/SIDE CHAIN LIQUID CRYSTALLINE COPOLYMERS

The synthesis and phase behaviour of chiral combined main/side chain liquid crystallinecopolymers containing pendant group constituted by chiral side group and trans-azobenzenemoiety with nitro end group are described. The formation of liquid crystalline polymorphism ofcopolymers is influenced by various contents of achiral side group.     

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.     

SYNTHESIS OF AN EPOXY-TERMINATED HYPERBRANCHED AROMATIC POLYESTER

An epoxy-terminated hyperbranched aromatic polyester (P3) was synthesized from a hyperbranched aromaticpolyester containing carboxylic acid end groups (P1), which was derived from the condensation polymerization of the AB_2monomer, 5-acetoxyisophthalic acid. Polymer P1 was converted into the polymeric acid chloride by reaction with thionylchloride. The acid chloride was reacted with ethanol and glycidol to form a poly(ethyl ester) (P2) and an epoxy terminatedmaterial (P3), respectively. The reaction conditions in each step of these processes had to be controlled very carefully toavoid unwanted cross-linking reactions. The characterization of products and intermediates, including molecular weightdistributions and thermal properties, are reported.     

SYNTHESIS AND CHARACTERIZATION OF MAIN CHAIN AROMATIC LIQUID CRYSTAL COPOLYESTERS WITH X-SHAPED AND ROD-SHAPED MESOGENIC UNITS

A series of main chain liquid crystal aromatic copolyesters with X-shapedand rod-shaped mesogenic units were synthesized via solution condensation polymerizationsof 4, 4'-(α,ω-octanedioyloxy)-dibenzoyl dichlorides with 2,5-bis(p-octanoxy benzoyloxy)-hydroquinone and diphenol. All of the copolyesters showed thermotropic liquid crystallinebehaviors through observations using DSC, polarized microscopy and X-ray diffraction.The melting point (T_m) and the isotropization temperature (T) change regularly withvarying the content of diphenol unit in the copolymers.     

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.     

条带织构装饰技术观察含T─型液晶基元的热致性聚芳酯液晶态的向错

采用条带织构装饰新技术研究了含Ｔ─型液晶基元的热致性聚芳酯液晶态的向错形态．经过培养的液晶样品无需剪切，淬火后便可呈现出围绕向错点取向排列的条带织构，而条带织构长轴的垂直方向正代表了液晶基元的指向矢方向，这样，在普通偏光显微镜下就能直接观察到这些条带织构装饰的强度Ｓ＝±１／２和Ｓ＝±１的向错，并观察到Ｓ＝－３／２的高强度向错和闭环状的反转壁．     

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.     

条带织构装饰技术观察含T─型液晶基元的热致性聚芳酯液晶态的向错

采用条带织构装饰新技术研究了含Ｔ─型液晶基元的热致性聚芳酯液晶态的向错形态．经过培养的液晶样品无需剪切，淬火后便可呈现出围绕向错点取向排列的条带织构，而条带织构长轴的垂直方向正代表了液晶基元的指向矢方向，这样，在普通偏光显微镜下就能直接观察到这些条带织构装饰的强度Ｓ＝±１／２和Ｓ＝±１的向错，并观察到Ｓ＝－３／２的高强度向错和闭环状的反转壁．     

EFFECTS OF CHAIN STRUCTURE OF POLYPYRROLONES ON THE ELECTRICAL PROPERTIES OF PYROLYZED POLYPYRROLONES

Three kinds of polypyrrolones (PMDA-DAB, PMDA-TADPE and DEDA-DAB) werepyrolyzed at high temperature in order to study the effect of the chain structure of polypyrro-lones on the electrical properties of the pyrolyzed polymers. Results show that the num-ber of fusing rings in the main chain of polymers has a little effect on the pyrolysis pro-cess, whereas, the ether bond in the main chain plays an important role during pyrolysis.Structure characterizations by elemental analyis, XPS spectra, X-ray diffraction and SEMimages indicate that because the ether bond is easy to break, it is difficult to form largearea planar network. This hampers the formation of the graphite-like structure in thepolypyrrolones containing ether bond even after being pyrolyzed at 1200℃.     

Py-GC/MS在VDF/CTFE共聚物链段结构和其裂解机理研究上的应用

用高分辨裂解气相色谱 质谱联用技术 (Py GC/MS)分析了VDF/CTFE(1∶4)链段结构和裂解机理。通过对实验条件的选择 ,找出了一套适合于VDF/CTFE(1∶4)共聚物的实验操作条件 ,且表明在此条件下所得的裂解谱图的重现性非常好。讨论了该共聚物具有无序的链段结构特征 ;确定此共聚物裂解机理为解聚断裂生成单体 ,还伴随有主链断裂形成低聚物     

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.     

SYNTHESIS OF NOVEL SOLUBLE AROMATIC POLYPYROMELLITIMIDE CONTAINING ORDERED 1,2,4-TRIAZINE IN THE MAIN CHAIN

A new heat-resistant, soluble polymer, poly(phenyl-1,2,4-triazine imide), has been prepared via a two-step methodof polycondensation of N,N'-bis(4-benzil)pyromellitimide and terephthalamidrazone in cresol, followed by curing at highertemperature. The rigid 1,2,4-triazine group increases the solubility of the polyimide so that the polymer is soluble in cresol,N-methyl-2-pyrrolidone (NMP), trifluoroacetic acid and concentrated sulfuric acid, etc. Thermogravimetric analysis (TGA)indicates that this novel polyimide has good thermal stability with a high decomposition temperature of 447℃ in air and of423℃ in N_2. It has a tensile strength of 107.4 MPa with an elongation at break of around 7.6%.     

STUDY ON SOLID STATE POLYCONDENSATION OF POLYETHYLENE TEREPHTHALATE COPOLYMERS

The kinetic data of solid state polycondensation of PET and its copolymers are determined.It is shown that the reaction rate of copolycondensation is higher than that of PET polyconden-sation, and increases with the comonomers content. But the reaction rate of copolycondensationin melt state of this kind of copolymers is lower than that of PET. It is considered that the chemi-cal reactivity of comonomer is the main factor which affect the polycondensation in melt state,whereas the aggregative structure of the polymer is the main factor in solid state. The crystallinity and crystallite size of the copolymers have been measured by X-ray method.     

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.     

含柔性间隔链段的芳香共聚酯热致性液晶高分子的结构研究

本文用富里叶红外光谱方法研究了一系列柔性间隔链段长度不等的芳香共聚酯热致性液晶高分子。测定了它们的变温光谱和偏振性质。并将谱带的变温行为与液晶转变相关联。结果表明,芳香共聚酯热致性液晶中液晶基元之间的相互作用很强而柔性间隔链之间的相互作用很弱。柔性间隔链段主要是伸直的反式构象。从一些谱带的二向色性估算了体系的有序度参数以及取向角。分子链的取向程度随柔性间隔链段长度的增加而减小。     

MORPHOLOGY OF A THERMOTROPIC AROMATIC POLYESTER

The crystalline morphology of a thermotropic aromatic polyester has been studied by microscopy techniques. Spherulites with ringed structure under polarizing micioscope were observed for solution cast specimens, They were composed of radially growing crystalline lamellae of thickness around 100. It was found that the molecules were packed in the thickness direction. Banded texture was observed in randomly packed domains for melt cast specimens. The bands have the same width and internal structure as those usually observed in oriented specimens of these polymers obtained by shearing their mesomorphic melt.     

STUDIES ON THE KINETICS OF PHASE TRANSITIONS OF A MAIN CHAIN THERMOTROPIC POLYESTER

The kinetics of phase transitions including a transition between mesophases were studied for a main-chain thermotropic polyester by means of DSC and depolarizing transmittance techniques. The isothermal process of these transitions was found to be described by the Avrami equation to high conversions. The Avrami exponents n are about 2,4, 5.3 and 2.2 for liquid crystallization, transition between mesophases and crystallization from mesophase respectively. The liquid crystallization from isotropic liquid phase occurs at very low undercoolings with high transformation rate. This behavior is explained as the results of the smaller value of the surface free energy for mesophase than that for crystallites which is evidenced by the very weak temperature dependence of liquid crystallization rate.