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.

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℃.

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.

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.

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.

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.

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.

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.

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.

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＂.

The Rheological and Extrusion Behaviour of Blends Based on Phenolphthalein Poly(ether-ether-sulfone)and Thermotropic Liquid Crystalline Polymer

A novel engineering thermoplastic, phenolphthalein poly(ether ether sulfone)(PES C) was blended with a commercial thermotropic liquid crystalline polymer(TLCP), Vectra A950, up to 30 weight percent of TLCP. A rheometrics dynamic spectrometer (RDS Ⅱ) and a CEAST capillary rheometer, a rheoscope 1000 were employed to investigate the melt rheology and extrusion behaviour at both the low and high shearing rates. The morphologies of the blends under different shearing were observed with a scanning electron microscope(SEM) and correlated to the observed rheology. The principal normal stress differences measured with cone and plate geometry give a temperature independent correlation for both blend and PES C when they are plotted against shear stress. But the extrudate swell of the blends showed a strong temperature dependence at each shear stress. The concentration dependence of extrudate swell shows a contrary behaviour to that of the inorganic filled system. A reasonable hypothesis based on the relaxation and disorientation of TLCP during flowing in the capillary and exiting was given to explain it. The melt fracture was checked after extrusion from capillary and was discussed.

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.

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.

CRYSTALLINE MORPHOLOGY IN A SERIES OF CH_(3)-SUBSTITUTED THERMOTROPIC AROMATIC POLYESTERS WITH EVEN AND ODD FLEXIBLE SPACERS

Crystalline morphology in a series of CH_(3)-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.Ln the case of crystallization from nematic melt two types of spherulites can be observed far the sample with even numbered spacers.For the sample with add numbered spacers spherulites can not be formed,but only irregular crystallites.

THE SPHERULITE-LIKE STRUCTURE OF MAIN CHAIN THERMOTROPIC AROMATIC COPOLYESTERS

A new spherulite-like structure of main chain thermotropic aromatic copolyesters formed in solution 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 thermotropic aromatic copolyesters formed from the casting solution (phenol/Cl2CH2CH2Cl2) is not a real crystal but only a high oriented arrangement of the macromolecular chains as a spherulite. This resulted from the interaction between the needle-like crystal of phenol and the rigid mesomorphic groups of molecular chain. The parallel packing of extended copolyester molecules along the needle-like crystal of phenol leads to the formation of the spherulite-like structure.

SYNTHESIS AND CHARACTERIZATION OF SOME THERMOTROPIC LIQUID CRYSTALLINE POLYAMIDES

A series of novel mesogenic polyamides containing a flexible pendent side group was synthesized by solution condensation polymerization. The new monomers, diacids and diamines containing flexible elements of different lengths, were also synthesized and characterized by H-1 NMR, mass spectroscopy and elemental analysis. The polymers were characterized by viscosity measurements, differential scanning calorimetry (DSC), X-ray diffraction and polarizing optical microscopy. These studies revealed that polyamides containing flexible elements of a sufficient length exhibited thermotropic liquid crystalline (LC) properties. The melting temperatures of this series of polymers were: particularly sensitive to the length of the flexible segment on the main chain and that of the flexible pendent ester side chain. Lyotropic LC behaviours were also observed in solution.

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.

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.