An exfoliation of organoclay in thermotropic liquid crystalline polyester nanocomposites

A thermotropic liquid crystalline polyester (TLCP) with an alkoxy side-group was synthesized from 2-ethoxyhydroquinone and 2-bromoterephthalic acid. Nanocomposites of TLCP with Cloisite 25A (C25A) as an organoclay were prepared by the melting intercalation method above the melt transition temperature (T_m) of the TLCP. Liquid crystallinity, morphology, and thermo-mechanical behaviors were examined with increasing organoclay content from 0 to 6%. Liquid crystallinity of the C25A/TLCP hybrids was observed when organoclay content was up to 6%. Regardless of the clay content in the hybrids, the C25A in TLCP was highly dispersed in a nanometer scale. The hybrids (0-6% C25A/TLCP) were processed for fiber spinning to examine their tensile properties. Ultimate strength and initial modulus of the TLCP hybrids increased with increasing clay content and the maximum values of the mechanical properties were obtained from the hybrid containing 6% of the organoclay. Thermal, morphological and mechanical properties of the nanocomposites were examined by differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA), polarized optical microscope, electron microscopes (SEM and TEM), and capillary rheometer.     

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.     

Wear and mechanical properties of reactive thermotropic liquid crystalline polymer/unsaturated polyester/glass fiber hybrid composites

To improve the performance of unsaturated polyester (UP) under cold‐heat alternate temperature, self‐synthesized reactive thermotropic liquid crystalline polymer (TLCP)‐methacryloyl copolymer (LCMC), UP, and glass fiber (GF) hybrid composites was prepared by molding technology. The apparent activation energy and crystal behavior analysis of LCMC/UP blends were investigated by Differential scanning calorimetry and X‐ray diffraction (XRD), respectively, the results showed that the addition of LCMC can reduce apparent activation energy and accelerate the curing reaction of UP, the XRD analysis indicated that the crystal phase of LCMC still exist in the blends after blending with UP. The effect of LCMC content on the properties of LCMC/UP/GF hybrid composites such as impact strength, bending strength, and ring‐on‐block wear were also investigated through static mechanical tests and wear tests. The mechanical properties of hybrid composites increased significantly because of the addition of LCMC. The wear tests showed that LCMC can improve the wear resistance of the UP/GF/LCMC hybrid composites even though the content of LCMC was at a relatively low level (5–7.5 wt %). This makes it possible to develop novel kind of UP‐based materials with good wear resistance for various applications. The Worn surface was observed by scanning electron microscopy (SEM) and the mechanism for the improvement is discussed in this paper. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3899–3906, 2007     

Effect of carbon nanofibers on the anisotropy of an aromatic thermotropic liquid crystalline polymer

The microstructure of a thermotropic liquid crystalline polymer (TLCP, Vectran V400 P) was investigated in the presence of vapor-grown carbon nanofibers. Percolation threshold was observed at ∼5 wt% carbon nanofibers. During processing, strong flows resulted in severe anisotropy of the semirigid rod-like TLCP molecules. For a given type of flow, however, the nanofibers were found to reduce the overall anisotropy of the TLCP nematic phase in the nanocomposite. We believe that nanofibers provide surface anchoring for the nematic phase that helps disrupt the high degree of molecular order in the TLCP matrix and reduces its anisotropy in the nanocomposite.     

Studies on thermotropic liquid crystalline polymers part XIII. Synthesis and properties of fully aromatic liquid crystalline poly(amide-ester)s

Four series of novel fully aromatic thermotropic liquid crystalline high molecular weight poly(amide-esters were prepared by direct polycondensation from terephthalic acid (TPA) and 2,6-naphthalene dicarboxlic acid with various aromatic diols and diamines in the presence of diphenyl chlorophosphate (DPCP), LiCl, and pyridine. The structures and thermal properties of the synthesized poly(amide-ester) s were examined by FTIR spectrum, wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermal optical polarized microscope and thermogravimetric analysis (TGA). The effects of the amounts and kinds of the aromatic diols and diamines (bisphenyl units, naphthalene and (un)substituted phenylene structures) on the molecular weight and thermal properties of the synthesized poly (amide-ester) s were investigated in this study. When a portion of the amide groups were replaced with the ester groups, most of the synthesized poly(amide-ester)s containing naphthalene or substituted hydroquinone units showed excellent mesophase and thermal stability, but the poly(amide-ester)s containing bisphenyl structures lost the mesophase behaviors. The P3 series of poly(amide-ester)s derived from TPA and 2,6-naphthalene dicarboxlic acid with phenylhydroquinone and various diamines possess liquid crystalline properties, even some of the diamines containing kink structures.     

Miscibility study on blend of thermotropic liquid crystalline polymers and polyester

The miscibility of thermotropic liquid crystalline polymers (TLCPs) and polyester blends was investigated with thermal and morphological analyses, as well as transesterification. TLCPs composed of 80 mol % para‐hydroxybenzoate (PHB) and 20 mol % poly(ethylene terephthalate) (PET) or 60 mol % PHB and 40 mol % PET, and polyesters such as PET and poly(ethylene 2,6‐naphthalate) (PEN) were melt blended in an internal mixer. DSC analyses were performed to investigate the thermal transition behavior and to obtain thermodynamic parameters. All the blends showed only a single glass‐transition temperature, which means they are partially miscible in the molten state. The Flory–Huggins interaction parameter was calculated employing the Nishi–Wang approach, and negative values were obtained except for the P(HB8‐ET2)/PEN blends. Transesterification was investigated using ¹H‐NMR, and the change of chemical shift compared to pure PET or P(HB‐ET)s was observed in the P(HB‐ET)/PET blends. An intermediate chemical shift value (4.83 ppm) was observed in the P(HB6‐ET4)/PEN blends, which indicates transesterification occurred. The fractured surface morphology of scanning electron micrographs showed that the interfaces between the LC droplets and matrix were not distinct. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1842–1851, 2003     

Microstructure of carbon nanofiber/thermotropic liquid crystalline polymer composites

The properties and microstructure of a thermotropic liquid crystalline polymer (TLCP, Vectran V400P) were investigated in the presence of carbon nanofibers (CNF). The electrical conductivity of TLCP increased with an addition of CNFs. The thermal analysis of pure TLCP and its composites revealed that a glass transition at ～ 110°C did not change significantly. However, a decrease of tensile modulus and strength was observed with the addition of CNFs. WAXD studies showed a decrease of Herman's orientation parameter, indicating reduction of anisotropy of TLCP. Further, the disruption of molecular orientation of TLCPs was inferred by SEM and TEM analysis. SEM micrographs revealed a fibrillar structure for pure TLCPs at a macro‐scale (2–5 μm). However, this structure was not observed in composites at the same scale even though micro‐size fibrils (0.05 μm) were found with the addition of CNFs. TEM micrographs displayed banded structures of pure TLCPs, but these structures were not significant in the vicinity of CNFs. These observations confirmed that a decrease of molecular alignment and disruption of fibrillar structure of TLCP, in the presence of nanofibers, are attributed to a significant decrease in tensile modulus and strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚丙烯/热致性液晶聚合物原位复合材料的研究进展

聚丙烯是一个通用塑料,为了提高聚丙烯的性能,拓宽其应用领域,人们对聚丙烯进行了改性研究.笔者简述了热致液晶聚合物原位复合改性聚丙烯的研究进展,并讨论热致液晶聚合物对聚丙烯结晶与熔融行为、微观结构、流变性及力学性能的影响,介绍了改进TLCP与PP之间相容性的常用方法.最后对TLCP/PP原位复合材料的发展提出一些看法.     

Development of co-continuous structure in liquid crystalline polyester

We investigated liquid crystallization of liquid crystalline polyester BB-5 during isothermal annealing by digital high-fidelity microscope and light scattering. A liquid crystalline spherical domain having a radius of micrometers appeared by annealing at around 180 °C. The domain grew dendritically in all directions. Neighboring liquid crystalline regions coalesced and then interconnected. The interconnected structure changed to a co-continuous two-phase structure with increasing ordering of the liquid crystalline phase, and the interface between the liquid crystalline phase and the isotropic phase became smoother over time. Liquid crystallization stopped before volume filling the whole space, and the liquid crystalline phase and isotropic phase coexisted. The liquid crystalline region became narrower with an increase in the temperature of the liquid crystallization. Such structural development is different from the liquid-liquid phase separation via spinodal decomposition, and it may be attributed to the segregation of non-liquid crystallizable low molecular weight molecules from the growth front by fractionation of the molecular weight distribution during the liquid crystallization in terms of the instability of the diffusion-controlled interface.     

A novel microstream injection molding method for thermotropic liquid crystalline polymers to promote mechanical isotropy: A matrixing microbeam X-ray study

The effects of flow-altering inserts and mold cavity geometry on the mechanical properties of an injection molded liquid crystalline polymer were studied to produce parts with properties approaching macroscopically isotropic state. By inserting fine metal mesh barriers to the gates of the mold cavities, a large number of highly oriented microstreams are produced. After their creation these highly oriented streams of differing flow vectors intertwine and this texture remains reasonably intact even after substantial shearing and extension history imparted on them during ensuing flow into the cavity. This method is effective in the interior away from the skin regions formed under the shearing flow during injection. The local molecular orientation was determined using a matrixing microbeam WAXS technique that allows precision movement of the sample in the microbeam X-ray. Samples produced with the 1.0 mm² mesh showed large variations in the local symmetry axis with respect to the machine as measured by microbeam X-ray diffraction incrementally from the edge to the core of the parts. In comparison, samples with no mesh insert showed only gradual changes in the tilt angle (angle between local symmetry axis and flow direction). The modulus and tensile strengths of all samples with the 1.0 mm² mesh inserts were found to approach virtual global mechanical isotropy.     

Thermal decomposition behavior of carbon nanotube reinforced thermotropic liquid crystalline polymers

Thermotropic liquid crystalline polymers (TLCP), 4‐hydroxybenzoic acid (HBA)/6‐hydroxyl‐2‐naphthoic acid (HNA) copolyester, and HNA/hydroxylbenzoic acid (HAA)/terephthalic acid (TA) copolyester reinforced by carbon nanotube (CNT) were prepared by melt compounding using Hakke internal mixer. The thermal behavior and degradation of CNT reinforced HBA/HNA copolyester and HNA/HAA/TA copolyester have been investigated by dynamic thermogravimetric analysis under nitrogen atmosphere in the temperature range 30 to 800°C to study the effect of CNT on the thermal decomposition behavior of the TLCP/CNT nanocomposites. The thermal decomposition temperature at the maximum rate, residual yield, integral procedural decomposition temperature, and activation energy for thermal decomposition was studied to investigate thermal stability of TLCP/CNT nanocomposites. The thermal stability of CNT reinforced HBA/HNA copolyester was increased by addition of a very small quantity of CNT and the residual weight was 42.4% and increased until 50.8% as increasing CNT contents. However, the thermal stability of CNT reinforced HNA/HAA/TA copolyester was decreased initially when a very small quantity of CNT added. The residual weight was decreased from 50.4% to 45.1%. After addition of CNTs in the TLCP matrix, the thermal stability of CNT reinforced HNA/HAA/TA copolyester increased as increasing content of CNT and the residual weight was increased until 53% as increasing CNT contents. The activation energy was calculated by multiple heating rate equations such as Friedman, Flynn‐Wall‐Ozawa, Kissinger, and Kim‐Park methods to confirm the effect of CNT in two different TLCP matrices. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Compatibilization by sulfonate ionomers in polyblends with thermotropic liquid crystalline polymers

It is shown by differential scanning calorimetry (DSC) measurements that lightly sulfonated polystyrene (SPS) is partially miscible with polysulfone (PSF), polycarbonate (PC), polyetherimide (PEI), and a thermotropic liquid crystalline polymer (LCP). Fourier transform infrared analysis confirms that the miscibility of SPS and PSF, and of SPS and PC, comes from the ion–dipole interaction between the sulfonate groups of SPS and the polar groups of PSF and PC, respectively. After the addition of SPS to LCP/PSF, LCP/PC, and LCP/PEI blends, this specific interaction leads to the compatibilization of SPS in these blends, which is revealed by inward glass transition temperature shifts of component polymers in DSC and dynamic mechanical analysis thermograms and by a much finer dispersion of the minor LCP phase in these matrix polymers. The utilization of SPS as the compatibilizer results in a stronger interfacial adhesion between LCP and matrix phases and improves the mechanical performances of LCP/PSF, LCP/PC, and LCP/PEI blends as well. Compared with ternary LCP/PSF, LCP/PC, and LCP/PEI blends with polystyrene as an inert third component, the ternary LCP/SPS/PSF, LCP/SPS/PC, and LCP/SPS/PEI blends have significantly enhanced tensile strengths and moduli, with acceptable processabilities at the same time. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2141–2151, 1998     

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     

In situ reinforced and flame-retarded polycarbonate by a novel phosphorus-containing thermotropic liquid crystalline copolyester

Polycarbonate (PC) was blended with various loadings of novel phosphorus-containing thermotropic liquid crystalline copolyester named PHDDT to form the in situ reinforced composites (PC/PHDDT) by flake extrusion. The morphology, thermal behaviors, tensile properties and flame-retardant performances of PC/PHDDT composites were investigated. Results suggested that fine deformation and microfibrillation of PHDDT in PC matrix could be formed during flake extrusion, which was confirmed by both the SEM observation and rheological analysis. With the increase of PHDDT content, the limiting oxygen index (LOI), tensile strength and storage modulus of the composites were enhanced simultaneously, along with the gradually decreased values of the peak heat release rate (PHRR) and the total heat released (THR), indicating the in situ reinforced and flame-retardant PC/PHDDT composites could be obtained.     

Synthesis and characterization of a thermotropic liquid crystalline hyperbranched polyester

BACKGROUND: Hyperbranched polymers have received increasing attention in the fields of medicine, homogeneous catalysis and materials science. Hydroxyl‐functional aliphatic polyesters are one of the most widely investigated families of hyperbranched polymers. The research reported here is based on the preparation of a novel hyperbranched polyester and the modification of its terminal hydroxyl groups by biphenyl mesogenic units. RESULTS: 2,2,6,6‐Tetramethylolcyclohexanol as a core and 8‐[4′‐propoxy(1,1‐biphenyl)yloxy]octanoic acid as a mesogenic unit were synthesized. A hyperbranched polyester (HPE) was synthesized in one step and subsequently substituted by reaction of its terminal hydroxyl groups with the biphenyl mesogenic units to yield a novel liquid crystalline hyperbranched polyester (HPE‐LC). The chemical structures of all compounds were confirmed using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopy. The thermal behavior and the mesogenic properties of the biphenyl mesogenic unit and HPE‐LC were investigated using differential scanning calorimetry, polarized optical microscopy and wide‐angle X‐ray diffraction. The results demonstrated that the degree of branching of the HPE is ca 0.63. Both HPE‐LC and the biphenyl mesogenic unit exhibit mesomorphic properties, but HPE‐LC has a lower isotropic transition temperature and a wider transition temperature range than the biphenyl mesogenic unit. CONCLUSION: A novel liquid crystalline hyperbranched polyester was successfully synthesized, which exhibits mesomorphic properties. This polymer has good solubility in highly polar solvents and good thermal stability. Copyright © 2009 Society of Chemical Industry     

Characterization of thermotropic liquid crystalline polyester/polycarbonate blends: Miscibility,rheology, and free volume behavior

Miscibility, rheology, and free volume properties of blends of thermotropic liquid crystalline polymers (TLCPs) (Vectra A950) and polycarbonate (PC) are studied in this work. Despite the unusual increase in T_g of the PC phase, the blends are found to be generally immiscible. Transesterification may occur during blending and be the cause of the increase of T_g of the PC phase and the partial miscibility of the blends at high TLCP concentrations. With regard to the melt rheology of these materials, according to a three‐zone model, dynamic moduli of Vectra A950 show plateau‐ and transition‐zone behavior, while PC exhibits terminal‐zone behavior. The blends show only terminal‐zone behavior at low Vectra A950 contents (≤50%) and terminal‐ and plateau‐zone behavior at higher Vectra A950 contents. The relaxation time of Vectra A950 is much longer than PC and the blends have relaxation times greater than additivity. Both the complex and steady shear viscosities of the blends increase with the addition of Vectra A950. This is attributed to interfacial association, which retards the reorientation and alignment of the Vectra A950 phase in the molten state. The Cox–Merz rule holds true for PC but not for Vectra A950 and the blends. Free volume properties on an angstrom scale evaluated by positron annihilation lifetime spectroscopy (PALS) indicate that Vectra A950 has smaller, fewer free volume cavities than PC and the variation of free volume behavior in the blends can be explained in terms of blend miscibility. The measured densities of the blends agree well with the free volume fractions of the blends determined from PALS. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2319–2330, 2000     

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     

Properties of a semi-crystalline and an amorphous thermotropic liquid crystalline polymer

The physical properties, thermal stability, rheology and tensile properties of a commercial semi-crystalline and an amorphous thermotropic liquid crystalline polymer (TLCP) have been investigated. Analysis by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) confirm the presence of a small melting endotherm and a glass transition in the former material. The as-received amorphous TLCP exhibits no obvious melting endotherm and a strong glass transition is detected. The flow and tensile properties of the semicrystalline polymer are dominated by the presence of the crystalline to nematic transition temperature. The properties of the amorphous TLCP appear to be governed by increasing mobility afforded by increasing temperature. Based on flow behaviour and further DSC analysis it has been shown that under appropriate annealing conditions the as-received amorphous TLCP can develop solid crystalline order.     

热致液晶共聚酯60PHB/PEN的合成及其表征

合成了对乙酰氧基苯甲酸与聚萘二甲酸乙二醇酯的热致液晶共聚酯(简称60PHB/PEN)。通过元素分析、红外光谱、DSC、热台偏光显微镜以及广角X射线衍射对其进行了结构、液晶性表征。实验表明,合成的共聚酯确系高度无规的PEN、PHB共聚酯,在某个温度范围内呈现向列型液晶的典型特征。     

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