SYNTHESIS AND CHARAOTERIZATION OF NOVEL THERMOTROPIO LIQUID ORYSTALLINE POLYESTERS BEARING NONLINEAR OPTICAL AZOBENZENE SIDE GROUP

A series of novel thermotropic liquid crystalline polyesters bearing nonlinear optical azobenzene side group were synthesized by high temperature solution polycondensation and their structures,thermal stability, phase transition behavior and crystallinity were characterized by IR,elemental analysis, TG-DTA, polarizing optical microscope (POM) equipped with a hot stage and X-ray diffraction techniques. The results demonstrate that all the synthesized polyesters exhibit nematic liquid crystalline phases and show relatively high glass transition temperatures and good thermal stability.

STUDY ON THE EFFECTS OF TLCP ON PYROLYSIS OF PET AND ITS RETARDANT MECHANISM

The flame retardancy of aromatic thermotropic liquid crystal phosphorus-containing copolyester,TLCP,on PET was investigated.The results show that the presence of TLCP promotes char formation of the substrate and enhances thermal stability of char,hence delay its decomposition.SEM pictures show that the char formed from PET/TLCP is more compact, therefore is more resistant to fire and heat than that from pure PET.Evolved gas analysis by I.R measurements indicates that TLCP would decompose to produce phosphor...

Odd-even Effect on Liquid Crystalline Behavior for C_3-Cyclotriveratrylene(CTV) Derivatives Containing Alkoxies with Different Lengths as Peripheral Groups

A series of bowlic cyclotriveratrylenes（CTV） with peripheral groups with different lengths were synthesized.These compounds were investigated by diferential scanning calorimetry and hot stage coupled polarizing microscopy.Several CTV derivatives show thermotropic liquid crystalline properties.The experimental results of their thermotropic liquid crystalline behavior indicate that the clear points,the entropy changes of melting points,the crystallization temperatures,and their entropy changes all exhibited an evident odd-even effect except the melting points,which decreased monotonously with the increase of the length of the alkoxy groups.The parameter values of CTVs with even number carbon atoms were larger than those of CTVs with odd number.When the length of alkoxyl chains was even longer,a monotonous decrease occured.Nevertheless,in the case of the entropy changes of both melting points and crystallization temperatures,the effect was valid for all the six species,and therefore,the whole curves presented as a zig-zag form.

Research on characterization of thermotropic polyurethane membrane of PDAG/BDO/MDI

Adopting Poly（ethylene glycol） adipate Dilpoly- （ethylene glycol）] adipate polydiglycol adipate glycol （PDAG）, 1,4-butanediol （BDO）, hydroxy silicone oil, methylene diphenyl diisocyanate （MDI） as the raw material, a new polyurethane elastic body can be made through prepolymerization. After measurement of the moisture permeability, adsorption quantity and mechanical properties of the membrane made with the elastic body, we also proofed its formula by infrared spectroscopy. The result showed that the moisture permeability of the membrane, with a certain intelligent thermotropic quality, will increase by 3 to 4 times when the temperature is between 25℃-45℃.

Liquid Crystalline Polymers XIII Main Chain Thermotropic Copoly (Arylidene-Ether)s Containing 4-Teriary Butyl-Cyclohexanone Moiety Linked with Polymethylene Spacers

A new homologous series of thermotropic liquid crystalline copoly(arylidene-ether)s based on 4-teriary butyl cyclohexanone moiety were synthesized by solution polycondensation of 4,4’-diformyl-α,ω-diphenoxyalkanes, Ia-d or 4,4’- diformyl-2,2’-dimethoxy-α,ω-diphenoxyalkanes IIa-d with the 4-teriary butyl-cyclohexanone III and cyclopentanone. A model compound IV was synthesized from the monomer III with benzaldehyde and characterized by elemental and spectral analyses. The inherent viscosities of the resulting polymers were in the range 0.22 - 0.92 dI/g. All the copoly(arylidene-ether)s were insoluble in common organic solvents but dissolved completely in concentrated H2SO4 and formic acid. The mesomorphic properties of these polymers were studied as a function of the diphenoxyalkane space length. Their thermotropic liquid crystalline properties were examined by DSC and optical polarizing microscopy and demonstrated that the resulting polymers form nematic mesophases over wide temperature ranges. The thermogravimetric analyses of those polymers were evaluated by TGA and DSC measurements and correlated to their structural units. X-Ray analysis showed that copolymers having some degree of crystallinity in the region 2q = 5° -60°. In addition, the morphological properties of selected examples were tested by Scanning electron microscopy.

Rheological behavior during thermotropic gelation of polyacrylonitrile concentrated solutions

Dynamic viscoelastic properties of polyacrylonitrile(PAN)/DMSO/H2O solutions with different H2O contents were studied as a function of temperature.These PAN solutions gradually became gel with decreasing temperature.The sol-gel transition took place at a critical gel temperature,at which the scaling law of G'(ω)～G″(ω)∝ωn held,allowing an accurate determination of the critical gel temperature by means of the frequency independence of the loss tangent.The gel point of PAN solutions increases with increasing H2O content.The scaling exponent n(=0.86) at the gel point is confirmed to be universal for PAN gels,which is independent of temperature,suggesting the similarity of the fractal structure in the critical PAN gels.

Synthesis and Characterization of Thermotropic Liquid Crystalline Complexes Containing Ferrocenyl Group

Four ferrocenyl long -chain alkyl β-diketonato zinc(Ⅱ) complexes with a general formulaZnL2 (L = C5H5FeC5an COCH COCnH2n+1.n= 6 - 9) were synthesized. These complexes were characterizedby elementary analysis, IR 1HNMR MS. polarizing microscopy with a heating stage and DSC. It wasfound that the complexes have thermotropic liquid crystalline properties. The type of the heteronuclearliquid crystalline metal complexes have not been reported so far.

ADVANCES IN LIQUID CRYSTALLINE POLYESTERS

Advances have been made in understanding the interactions of composition, molecular weight, liquid crystallinity,orientation, and three-dimensional crystallinity on the properties of injection-molded and melt-spun liquid crystalline polyesters (LCP's). Two classes of potentially low-cost LCP's were compared:(1) semiflexible LCP's prepared from 1,6-hexanediol and the dimethyl ester of either trans-4, 4'stilbenedicarboxylic acid or 4.4 ' biphenyldicarboxylic acid and (2) all-aromatic LCP's prepared from terephthalic acid, 2, 6-naphthalenedicarboxylic acid, the diacetate of hydroquinone, and the acetate of p-hydroxybenzoic acid. The effects of composition on the plastic properties of the 4-component all-aromatic LCP's were determined with the aid of a 3 x 3 factorial statistically designed experiment, the generation of equations with a computer program, and the plotting of three-dimensional figures and contour diagrams. The effects of absolute molecular weight (M_w) on the tensile strengths of the semiflexible LCP's and one of the all-aromatic LCP's having an excellent balance of plastic properties were also compared, and it was observed that the semiflexible LCP's required M_w's about 4 times higher than the all-aromatic LCP to attain a given strength. Persistence lengths and molecular modeling were used to explain these differences.

Studies on Blends of Nylon 6 and a Thermotropic Liquid Crystalline Polyarylester(Ⅱ)——Morphology and Rheology

Blends of nylon 6 (PA6) and a semirigid thermotropic liquid crystalline polyarylester (THH) were prepared by coprecipitation. The changing of the morphology of the blends with their compositions was observed by means of a polarizing microscope and scanning electron microscope. The THH phases in the blends changed gradually from spherical droplets to fibrils with the increase of THH content. The flow behavior of the blends are quite different from that of the parent polymers and a very dramatic reduction in the melt viscosity of blends containing 5% THH was observed. The formation possibility of in-situ reinforcement composites of PA6 blends with a semirigid LCP is discussed in the present paper.

THERMAL DEGRADATION OF THERMOTROPIC LIQUID CRYSTALLINE TERPOLYESTERS BASED ON VANILLIC ACID, p-HYDROXYBENZOIC ACID AND POLY(ETHYLENE TEREPHTHALATE )

Nine thermotropic liquid crystalline terpolyesters based on vaniUic acid(V), p-hydroxybenzoic acid(H) and poly(ethylene terephthalate)(E) were investigated by thermogravimetry to ascertain their thermostability and the kinetic parameters for thermal degradation. Overall activation energy data of the degradation had been calculated over the range 5 ～ 70% weight loss. The temperatures and the activation energy of the degradation lie in the ranges of 384 ～ 394 ℃ at a heating rate of 1℃/min and 176 ～ 205 KJ/mol at the weight loss of 5%, respectively, which suggests that the terpolyesters have good thermostability.

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.

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.

STUDIES ON THE MORPHOLOGY OF THERMOTROPIC POLYESTER DURING TRANSITIONS BETWEEN ISOTROPIC AND ANISOTROPIC MELTS

The morphology of a thermotropic aromatic polyester during the transitions between isotropic and anisotropic melts was studied by means of polarizing microscopy and small angle light scattering techniques. Both transition processes were found to be composed of the initiation of a new phase at local places of the old phase matrix and the growth of the new phase domains. A change of Hv scattering patterns was observed in the transition temperature ranges and was explained as the result of heterogeneity of the mesophase system, but not the change in ordering of a homogeneous mesophase.

SYNTHESIS AND CHARACTERIZATION OF AROMATIC LIQUID CRYSTALLINE COPOLYESTERS WITH REGULAR SEQUENCE STRUCTURE

Several novel aromatic liquid crystalline copolyesters with regular sequence structure were prepared by melt Sehotten-Baumann polycondensation via complex monomer. Polarizing microscope with hot stage, thermal analysis and X-ray diffraction were used to investigate the structure and properties of the copolyesters. The effects of structural units, such as flexible spacer, noncolinear meta-linked phenylene unit, crankshaft unit, kink with flexible bridging unit and various substituted benzene rings on melting temperature of aromatic copolyesters were studied and discussed on the basis of crystalline structure of the polymers.

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.

MORPHOLOGICAL STUDIES ON THERMOTROPIC LIQUID CRYSTALLINE POLYESTER——MORPHOLOGY OF SHEAR ORIENTED FILMS

The morphology of shear-oriented films of a thermotropic liquid crystalline polyester containing a triad ester mesogenic unit and a flexible spacer has been investigated in details. The formation conditions and process, the fine structures and the relaxation process of mat structure in the oriented films have been observed and discussed.

STUDY ON THE PHASE TRANSITION KINETICS OF THERMOTROPIC LIQUID CRYSTALLINE AROMATIC-ALIPHATIC COPOLYESTER

The phase transition kinetics of thennotropic liquid crystalline aromatic-aliphatic regular copolyester: were studied by DSC. By means of Kissinger's method the kinetic equation and parameters including activation energy, rate order and preexponential factor for phase transition from nematic to isotropic were obtained. The activation energy from crystal to nematic was also presented.

EVIDENCE FOR THERMOTROPIC LIQUID CRYSTALLINITY OF A FUSIBLE POLYDIACETYLENE

The thermotropic liquid crystalline behavior of a fusible polydiacetylene has been studied by using polarizing optical microscopy and wide angle X-ray diffraction. It was found that the typical threaded texture can exhibit in the melt and the banded texture can be observed when applied a gentle shear to the melt. The results indicate that this polydiacetylene is really a thermotropic liquid crystalline polymer.

Synthesis and properties of novel thermotropic liquid crystalline copoly(ester-imide)s

Four novel copoly（ester-imide）s based on 3,3′,4,4′-biphenyltetracarboxylic dianhydride, bis（trimellitic acid anhydride） phenyl ester and di-p-aminophenyl ester of dicarboxylic acids were synthesized via two-step method in order to investigate whether two imide mesogenic units with different conformation and polarity could control the formation of LC-phase. Polarizes light microscopy （PLM） and differential scanning calorimetry （DSC） have shown that three polymers formed the nematic phase with ＂thread schlieren texture＂ and a polymer formed the nematic phase with ＂Inversion walls texture＂.

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.