Improved processing of thermotropic liquid crystalline polyesters

A series of thermotropic liquid crystalline polyesters based on p-hydroxybenzoic acid, terephthalic acid, 2,6-dihydroxynaphthalene and containing small amounts of either Bisphenol A, 2,7-dihydroxynaphthalene, or polyethylene terephthalate (PET) as comonomers were prepared. The latter three materials were investigated as a means of lowering the spinning temperature of the base polymer without sacrificing properties. Samples containing 1–2.5% Bisphenol A or 2.5–5% 2,7-dihydroxynaphthalene retained most of the properties (modulus fell slightly), but spinning temperature reduction was minimal. Polymers containing 2.5–5% PET retained full properties at spinning temperatures 60–80°C below the control.     

Synthesis and characterization of cholesteric thermotropic liquid crystalline polyesters

Cholesteric liquid crystalline polyesters were successfully synthesized from isosorbide, methyl hydroquinone, and isophthaloyl chloride. Homo/copolyesters were synthesized by the solution polycondensation method, for which a mild organic base such as pyridine was employed. Inherent viscosities of polyesters P‐3–P‐5 were in the range of 0.31–0.39 dL/g at 25°C in chloroform, and polyesters P‐1 and P‐2 were insoluble in chloroform. Homo/copolyesters based on isosorbide, methyl hydroquinone, and isophthalic acid had thermal stability at more than 300°C on the basis of 10% weight loss. The thermotropic liquid crystalline properties were examined by differential scanning calorimetry and polarizing optical microscopy. Wide‐angle X‐ray diffraction study demonstrated that polyesters P‐1, P‐2, and P‐3 were semicrystalline, whereas the degree of crystallinity of polyesters P‐4 and P‐5 was less than 5%. Copolyester P‐4 showed formation of a yellow iridescent streak at 209°C on heating and development of a Grandjean texture at 270°C on heating. These are typical textures of the cholesteric liquid crystalline phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1232–1237, 2007     

Novel thermotropic liquid crystalline polyphosphonates

Main chain liquid crystalline polyphosphonates containing semi-flexible phenylester mesogen with even number of methylene spacers (2-10) have been synthesized. The monomers and polymers were characterized by IR, ¹H, ¹³C and ³¹P NMR spectroscopy. The spectral details are in accordance with the structures. All the polymers were exhibited liquid crystalline property in the Hot stage optical polarized microscope (HOPM). DSC thermal analysis confirms the mesophase formation for all the polymers. The grain size of the liquid crystalline mesophase is increasing with increasing methylene chain. T_g, T_m and T_i of the polymers decreased with increase in spacer length. The T_g of these phosphorus-containing polymers is much lower than that of non-phosphorus polymers containing triad ester mesogens. Energy minimized structures for the molecules which mimic the polymer chain suggests that the reduction in T_g may be due to entanglement raised by incorporation of phosphorus heterogeneity.     

Modification of the processing window of a thermotropic liquid crystalline polymer by blending with another thermotropic liquid crystalline polymer

This paper is concerned with properties and processing performance of two thermotropic liquid crystalline polymers (TLCPs) produced by DuPont (HX6000 and HX8000) with widely varying melting points and blends of these two TLCPs. This work was carried out in an effort to develop a TLCP suitable for generating poly(ethylene terephthalate) (PET) composites in which the melting point of the TLCP was higher than the processing temperature of PET. Strands of the neat TLCPs and a 50/50 wt % TLCP–TLCP blend were spun and tested for their tensile properties. It was determined that the moduli of the HX8000, HX6000, and HX6000–HX8000 blend strands were 47.1, 70, and 38.5 GPa, respectfully. Monofilaments of PET–HX6000–HX8000 (50/25/25 wt %) were spun with the use of a novel dual extruder process. The strands had moduli as high as 28 GPa, exceeding predictions made using the rule of mixtures and tensile strengths around 275 MPa. The strands were then uniaxially compression molded at 270°C. It was found that after compression molding, the modulus dropped from 28 GPa to roughly 12 GPa due to the loss of molecular orientation in the TLCP phase. However, this represents an improvement over the use of HX8000. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2209–2218, 1999     

Thermal decomposition kinetics of thermotropic liquid crystalline polyesterimides

We investigated the thermal decomposition behavior of three groups of polyesterimides that had been synthesized from different compositions of monomers that were added in different. We characterized these polymers with thermogravimetric analysis (TGA) and calculated the apparent activation energy (E_a) associated with the thermal decomposition process by the Ozawa method. The results showed that the E_a of the polyesterimides was correlated with the length of the methylene spacer and the content of the 4,4′‐dihydroxybenzophenone monomer. The polyesterimide with four methylene spacers in the main chain had a higher E_a than that with six methylene spacers. The polyesterimide with a higher 4,4′‐dihydroxybenzophenone content provided better thermal stability. The E_a of the polyesterimides also depended on the sequence in which the monomers were added during the copolycondensation process. The E_a of these polyesterimides followed the order: p‐hydroxybenzoic acid added first > p‐hydroxybenzoic acid mixed 4,4′‐dihydroxybenzophenone adding > 4,4′‐dihydroxybenzophenone added first. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2467–2472, 2005     

Rheological properties of thermotropic liquid crystalline aromatic copolyesters

A series of thermotropic liquid crystalline polyesters based on p-acetoxybenzoic acid, naphthalene dicarboxylic acid, hydroquinone diacetate, and poly(ethylene terephthalate) were prepared via melt polycondensation. The anisotropic melts were studied by means of thermal optical testing, differential scanning calorimetry, scanning electron microscopy. X-ray diffraction, and rheological methods. It was found that the copolyesters in the mesomorphic state exhibit drastic shear-thinning and the experimental results indicate that the non-Newtonian Index n is in the range of 0.17 to 0.50, the flow-activation energies ΔE_η are 297.1 to 182.0 KJ/mol over the shear rate of 10 to 1000 S^?1 at temperature 225 to 270°C; and the mesomorphic copolymers are readily oriented during processing, resulting in highly oriented as-spun fibers.     

Crystallization morphology of a thermotropic liquid crystalline polymide

Crystallization morphology of an aromatic thermotropic liquid crystalline polyimide was studied by means of polarized light microscopy. The polyimide was synthesized from 1, 2, 4, 5-benzenetetracarboxylic dianhydride (PMDA) and 1, 3-bis[4'(4′ aminophenoxy) cumyl] benzene (BACB), which exhibited three exothermic peaks at onset temperatures of 292, 279, and 250°C in the DSC cooling curve. The results of polarized light microscopy revealed that the polyimide quenched from 350°C in air exhibited fine structure, frozen liquid crystalline texture. The liquid crystalline texture disappeared when the sample was heated to 298°C. However, the polymer melt still exhibited, to some degrees, birefringence until the temperature reached 340°C, where the polyimide was in the truly isotropic state. Isothermal crystallization experiments were carried out at both the isotropic temperature range and the non-isotropic temperature range. Two types of negative spherulites with lamellar structure and positive needle-like crystals formed from the isotropic melt have been observed. Interestingly, with a further decrease of the crystallization temperature to the liquid crystalline state temperature, the whole field was covered by the liquid crystalline texture. However, if the sample was kept at 286°C for a long time, and then reheated to 305°C to melt the liquid crystalline phase, negative spherulites with loose structures formed from the liquid crystalline state could be observed. Surprisingly, if the sample was kept at 305°C for a period of time, further crystallization could be observed using the spherulites formed at 286°C as nuclei. Composite spherulites were developed if the low-high temperature crystallization process was repeated.     

Self-Reinforced composites of two thermotropic liquid crystalline polymers

Blends of two thermotropic liquid crystalline polymers (LCP) based on 6-oxy-2-naphthoyl and p-oxybenzoyl moieties and p-oxybenzoyl, terephthaloyl and hydroquinone moieties have been studied. The blends were prepared by melt mixing using a twin screw extruder. Thermal, rheological, mechanical, and morphological studies were carried out. Based on the dynamic mechanical thermal analysis and the morphological observations, the blends are found to be immiscible. The viscosity ratios of pure LCP melts exceed values of 10 over a wide range of shear rates, with the viscosity of the blends lying between those of the pure components. The prepared blends are shown to be self-reinforced composites in which one LCP enhances the molecular orientation of the other. Studies of the injection molded bars by scanning electron microscopy indicate a complicated hierarchical morphology with microfibrils of submicron level in diameter, bundled, and intertwined into fibrils of a substantially larger diameter. Due to self reinforcement, impact and tensile properties of the blends show significant synergism when compared to those of the pure LCP components. The properties obtained are remarkably higher than those known for any high performance engineering thermoplastics.     

热致性液晶聚氨酯的合成及性能

以1,4-双（对羟基烷氧基苯甲酸）苯酯分别与2,4-甲苯二异氰乙酸酯（2,4-TDI）、二苯甲烷-4,4’-二异氰酸酯（MDI）反应制得聚氨酯。运用差热扫描量热分析仪（DSC）、偏光显微镜（POM）对其进行了表征。结果表明,合成的聚氨酯产物在一定温度范围内均为热致性向列型液晶体,其转变温度随着间隔基柔顺性的增加呈下降趋势。     

Mechanical properties and morphology of polymer blends of poly(ethylene terephthalate) and semiflexible thermotropic liquid crystalline polyesters

Two thermotropic liquid crystalline polyesters (TLCPs) with long flexible spacer groups in the main chain were prepared by melt polymerization: one was a homopolymer with only decane groups (LCPHO) and the other was a copolymer with hexane or decane groups (LCPCO) between mesogen units. These polyesters were blended with a matrix polymer of poly(ethylene terephthalate) (PET). Scanning electron microscopy (SEM) revealed the excellent interfacial adhesion between polyester and PET, and the large aspect ratio of polyester microfibrils in the blend fiber made by extruding and drawing the blend through a die. The aspect ratio was estimated by using the modified Halpin-Tsai equation. The fiber with LCPHO showed more extensive fibril formation than that with LCPCO.     

Synthesis and characterization of sulfonated liquid crystalline polyesters

Liquid crystalline polyesters based on hexanediol, dimethyl 4,4′‐biphenyldicarboxylate, and various levels of dimethyl 5‐sodiosulfoisophthalate (0–20 mol%) were prepared using a conventional melt polymerization process. The presence and quantification of the ionic functionality was surveyed using ¹H NMR spectroscopy. Solution viscosities and corresponding molecular weights decreased when the ionic monomer concentration exceeded a critical value (higher than 3 mol%). Differential scanning calorimetry indicated a maximum in the isotropic transition temperature versus ionic modification at approximately 10 mol%. Dynamic mechanical analysis indicated that the glass transition temperature was suppressed due to ionic association at high concentrations (greater than 3 mol%) of ionic functionality. Polarized light microscopy and wide‐angle X‐ray diffraction were used to identify the smectic liquid crystalline and crystalline phases. © 2002 Society of Chemical Industry     

Rheology and structure of liquid crystalline alkylenearomatic polyesters

The rheological, thermodynamic and structural properties of two liquid crystalline polyesters—poly(oxyfumaroyloxy- 1,4-phenylene carbonyloxyalkyleneoxycarbonyl- 1,4-phenylene)s with six and ten methylene groups (PES-6 and PES- 10, respectively) and a statistical copolyester (co-PES) have been investigated. It has been shown that they all form a smectic LC-phase. The change from homopolyesters to co-PE S expands the temperature range of the LC-state. The high sensitivity of the structure to the prehistory in the melt state is typical for such copolymers. Prolonged heating leads to rearrangement of the co-PES crystalline structure and a drastic increase in viscosity. The orientation of these polymers during flow was investigated. It was shown that a high level of molecular orientation of the smectic layers, perpendicular to the direction of flow, was realized at high shear stresses. In the melt region, the existence of a metastable network with junctions of crystalline nature hinders the flow of the homo- and copolyesters. The structure of the unit cell of the crystallites depends on the composition and thermal history.     

Characterization of thermotropic liquid crystalline polyester/polysulfone blends

The morphology, rheology, and mechanical properties of blends of polysulfone (PSF) with up to 65% of a wholly aromatic liquid crystalline polymer (LCP) were investigated. In injection molded specimens a skin-core morphology was observed with the LCP minor phase oriented in the skin and globular in the core. Scanning electron microscopy of fractured surfaces showed sharp phase boundaries, suggesting low interfacial adhesion. The neat PSF and blends with low amounts of LCP exhibited a low shear Newtonian plateau not observed in the blends with high LCP levels. The addition of LCP to PSF resulted in an increase in stiffness, a small increase in tensile strength, and a significant improvement in processability.     

Measurement of molecular orientation in thermotropic liquid crystalline polymers

Procedures for obtaining molecular orientational parameters from wide angle X-ray scattering patterns of samples of thermotropic liquid crystalline polymers are presented. The methods described are applied to an extrusion-aligned sample of a random copolyester of poly(ethylene terephthalate) (PET) and p-acetoxybenzoic acid. Values of the orientational parameters are obtained from both the interchain and intrachain maxima in the scattering pattern. The differences in the values so derived suggest some level of local rotational correlation     

Blends of thermotropic liquid crystalline polyesters and poly(butylene terephthalate): Thermal,mechanical, and morphological properties

Blends of poly(butylene terephthalate) (PBT) with three different thermotropic liquid crystalline polyesters (TLCPs) were prepared. The first TLCP (HBH-6) consists of diad aromaticester type mesogenic units and the hexamethylene spacers along the main chain, and the second (TB-S6) is a wholly aromatic polyester TLCP having alkoxy side groups on the terephthaloyl moiety. The last (TR-4,6) is an LC copolymer comsisting of triad aromatic ester type mesogenic units and two differents spacers; tetramethylene and hexamethylene units. Blends of TLCP with PBT were melt spum at different LCP contents and differnt draw ratios to produce monofilaments. For the HBH-6/PBT and TB-S6/PBT blends, the ultimate tensile strength showed a maximum value at the 5 wt% level of LCP in the blends, and then it decreased when the LCP content was increased up to 20%. On the other hand, the initial modulus monotonically increased with increasing LCP content in all cases. The blends with TB-S6 showed the highest tensile properties of the three blends systems. This can be ascribed to the highest rigidity of the polymer chain, which still carries relatively long alkoxy substituents that promote sufficient adhesion between the LCP and PBT matrix. When compared with the PBT fiber itself, the fibers obtained from the 5% TB-S6/PBT blends exhibited an improvement in tensile strength by > 25% and in tensile modulus by ～ 200%.     

Thermotropic liquid crystalline polyesters containing naphthalenic mesogenic groups

Summary Recently, the use of naphthalene in liquid crystalline compounds has become more commonplace primarily in the industrial research into LC polymers with wholly aromatic structures. A large number of compositions have appeared in the patent literature, and have been well summarized in several recent articles. Even though a large number of LC naphthalene-containing copolyesters have been prepared and reported, much of this work deals with wholly aromatic systems which include no flexible spacers. In order to investigate the effects that the naphthalene structure has on liquid crystalline behaviour, a series of low molecular weight model compounds and polymers with flexible spacers were synthesized and characterized.     

Reinforcement of polyamide 6 with thermotropic liquid crystalline polymer

The in-situ composites of polyamide 6 (PA 6)/liquid crystalline polymer (LCP) were investigated from the standpoint of fibrillation of LCP to develop a new high performance gear material for heavy load use that is superior to conventional plastic gears made of polyacetal (POM). LCP used was a wholly aromatic copolyester. PA 6 was chosen as the matrix polymer because of its excellent fatigue resistance. Extrusion of PA 6 added with LCP from 10 to 30 vol% was carried out at a temperature between 260 and 290°C by a twin screw extruder and take-up equipment. Insitu fibrillation of LCP droplets, which were dispersed in PA 6 matrix, took place during the process. Injection molding of the composites was followed at a temperature below the softening point of LCP fibrils so as to keep the fibrils as extruded. Key factors for fibrillation of LCP were found as follows: (1) control of stress relaxation of LCP when the melt passes through the die-head, (2) the optimum temperature of nent, (3) the optimum LCP content, and (4) addition of a small amount of 3rd component. A gear made of in-situ composite of PA 6/LCP (30 vol%) added with 2-functional epoxy resin (2.5 phr) was found to bear a load about 1.2 times heavier than a POM gear.     

The rotational molding of a thermotropic liquid crystalline polymer

Thermotropic liquid crystalline polymers (TLCPs) exhibit a number of mechanical and physical properties such as excellent chemical resistance, low permeability, low coefficient of thermal expansion, high tensile strength and modulus, and good impact resistance, which make them desirable as a rotationally molded storage vessel. However, there are no reports in the technical literature of the successful rotational molding of TLCPs. In this article, conditions are identified that lead to the successful rotational molding of a TLCP, Vectra B 950. First, a technique was developed to produce particles suitable for rotational molding because TLCPs cannot be ground into a free‐flowing powder. Second, because the viscosity at low shear rates can be detrimental to the sintering process, coalescence experiments with isolated particles were carried out to determine the thermal and environmental conditions at which sintering should occur. These conditions were then applied to static sintering experiments to determine whether coalescence and densification of the bulk powder would occur. Finally, the powders were successfully rotationally molded into tubular structures in a single axis, lab‐scale device. The density of the molded structure was essentially equivalent to the material density and the tensile strength and modulus were approximately 18 MPa and 2 GPa, respectively. POLYM. ENG. SCI., 45:410–423, 2005. © 2005 Society of Plastics Engineers     

Carboxylated multiwall carbon nanotube-reinforced thermotropic liquid crystalline polymer nanocomposites

Thermotropic liquid crystalline polymer (TLCP) nanocomposites reinforced with carboxylated multiwall carbon nanotube (c-MWCNT) were prepared through melt compounding in a twin screw extruder. The thermal stability of TLCP/c-MWCNT nanocomposites increased with even a small amount of c-MWCNT added. The rheological properties of the TLCP/c-MWCNT nanocomposites were depended on the c-MWCNT contents. The contents of c-MWCNT have a slight effect on the complex viscosity of TLCP/c-MWCNT nanocomposites due to the high-shear thinning of TLCP. The storage modulus of TLCP/c-MWCNT nanocomposites was increased with increasing c-MWCNT content. This result can be deduced that the nanotube–nanotube interactions were more dominant, and some interconnected or network-like structures were formed in the TLCP/c-MWCNT nanocomposites. Incorporation of very small amount of c-MWCNT improved the mechanical properties of TLCP/c-MWCNT nanocomposites, and this was attributed to the reinforcement effect of c-MWCNT with high aspect ratio and their uniform dispersion through acid treatment in the TLCP matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008