Structure and properties of thermotropic liquid crystal polymer and poly(ethylene 2,6‐naphthalate) blend fibers

BACKGROUND: The melt blending of thermotropic liquid crystal polymers (TLCPs) using conventional thermoplastics has attracted much attention due to the improved strength and tensile modulus of the resulting polymer composites. Moreover, because of their low melt viscosity, the addition of small amounts of TLCPs can reduce the melt viscosity of polymer blends, thereby enhancing the processability. RESULTS: In this study, TLCP/poly(ethylene 2,6‐naphthalate) (PEN) blend fibers were prepared by melt blending and melt spinning to improve fiber performance and processability. The relation between the structure and the mechanical properties of TLCP/PEN blend fibers and the effect of annealing on these properties were also investigated. The mechanical properties of the blend fibers were improved by increasing the spinning speed and by adding TLCP. These properties of the blend fibers were also improved by annealing. The tensile strength of TLCP5/PEN spun at a spinning speed of 2.0 km h^?1 and annealed at 235 °C for 2 h was about three times higher than that of TLCP5/PEN spun at a spinning speed of 0.5 km h^?1. The double melting behavior observed in the annealed fibers depended on the annealing temperature and time. CONCLUSION: The improvement of the mechanical properties of the blend fibers with spinning speed, by adding TLCP and by annealing was attributed to an increase in crystallite size, an increase in the degree of crystallinity and an improvement in crystal perfection. The double melting behavior was influenced by the distribution in lamella thickness that occurred because of a melt‐reorganization process during differential scanning calorimetry scans. Copyright © 2007 Society of Chemical Industry     

Novel CO2 laser drawing of thermotropic liquid crystal polymer and poly(ethylene 2,6‐naphthalate) blend fibers

Thermotropic liquid crystal polymer (TLCP)/poly(ethylene 2,6‐naphthalate) (PEN) were prepared by a melt blending, and were melt spun by a spin‐draw process. In this study, we suggest novel drawing technology using the CO₂ laser that can directly and uniformly heat up fiber inside to prevent the formation of ununiform structures in conventional heat drawing process. The properties of the heat/laser drawn TLCP/PEN blend fibers were superior to those of any other handled fibers, and were rather more excellent than those of TLCP/PEN blend fibers annealed at 135°C for 10 min. It was confirmed that the CO₂ laser drawing made it possible to achieve the optimal drawing effect by draw ratio. The combined heating and CO₂ laser‐drawing method has a great potential for industrial applications as a novel fiber‐drawing process, and it can also be applied continuously to conventional spin‐draw system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 205–211, 2007     

Steady viscosity of a polymer/liquid crystal biphasic system

Steady shear viscosities of blends of poly(butyl acrylate) and cholesteryl oleyl carbonate were studied under a cone and plate fixture. Unique shear behavior was observed for the polymer/low molar mass liquid crystal mixture. The viscosity of the liquid crystal‐rich phase increases with polymer content until a maximum is reached. The height of the viscosity maximum decreases with the magnitude of the shear stress and disappears when the stress reaches 200 Pa. Addition of liquid crystal to the polymer‐rich phase causes a viscosity reduction, and at higher stress levels, the viscosity reduction becomes more effective with the same amount of liquid crystal addition. The viscosity reduction may be related to the fibril morphology of the liquid crystal and the viscosity maximum can be interpreted by the emulsion effect being counteracted by a viscosity reduction effect. A shear‐thickening behavior was observed in the intermediate shear rates for the blends with a volume fraction of poly(butyl acrylate) between 9.4 and 49.8%. This is a novel liquid–liquid system that exhibits a shear thickening behavior. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 25–30, 2004     

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     

Morphology and thermal properties of two polymethacrylates modified by a polymer liquid crystal

We have studied blends of a polymer liquid crystal (PLC) with poly(cyclohexylethyl methacrylate) (PCHEMA) or poly(cyclohexylpropyl methacrylate) (PCHPMA). The PLC is PET/0.6PHB where PET = poly(ethylene terephthalate), PHB = p-hydroxybenzoic acid and 0.6 is the mole fraction of the latter in the copolymer. The microstructure was studied by scanning electron microscopy (SEM). PCHEMA + PLC (20 wt% of the latter, blend E) has a fine texture with LC islands evenly distributed in the matrix and good adhesion between the phases resulting from their partial miscibility. The PCHPMA + PLC (20 wt% of the latter, blend P) shows only limited compatibility. The SEM results are confirmed by values of the glass transition temperatures T_g determined via thermal mechanical analysis. The T_g value of the blend E is shifted towards the T_g of PLC; T_g of blend P is practically equal to that of PCHPMA. The linear isobaric expansivity α_L values for both blends are lower than the respective values for pure PCHPMA and PCHEMA. Thermal stabilities of the blends determined by thermogravimetry are also better than those of pure polymethacrylates. The temperature of 50% weight degradation for blend E is higher than that for pure PCHEMA by more than 60 K Copyright © 2004 Society of Chemical Industry     

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     

Novel blends made of ionic naphthalene thermotropic polymer and poly(ethylene terephthalate)

Novel blends made of ionic naphthalene thermotropic polymer (NTP) and poly(ethylene terephthalate) (PET) have been prepared by melt mixing. Homogeneous blends were formed when a small amount (5 wt%) of ionic NTP was blended with PET; but, phase separation occurred at a higher composition of the ionic NTP (10 wt%). Both the stiffness and the strength are enhanced in all the blends studied as compared with PET. A remarkable increase in ductility and toughness is noted during necking in these blends. Enhancement in tensile properties and good homogeneity of the blends at low composition (5 wt%) are attributed to ion-dipole interactions between the ionic groups of the ionic NTP and the dipolar units of the PET. It is suggested that ionic NTP chains not only act as reinforcer in the homogeneous blends, but also serve as a nucleating agent to increase crystallinity and as a good stress transfer agent to ease an inhomogeneous deformation process during necking of the PET matrix under tensile stress.     

Spinnability and physical properties of in situ composite fibers based on thermotropic liquid crystalline polymer

In situ composite fibers based on poly(ethylene 2,6‐naphthalate) (PEN) and a thermotropic liquid crystalline polymer (Vectra A950) were prepared using a single‐screw extruder. The fibers were taken up at selected speeds. The spinnability, thermal behavior, mechanical properties, and morphologies of the PEN/Vectra A950 blend were investigated. The results showed that the PEN/Vectra A950 blends were partly miscible, and the miscibility increased with the increased concentration of Vectra in the blend. The DSC measurements indicated that Vectra enhanced the crystallization process of PEN by performing as a nucleating agent. The Instron tensile property study, coupled with scanning electron microscopy, revealed that the mechanical properties of the PEN matrix were significantly improved when Vectra existed as long and continuous fibrils. The laser Raman results showed that the Vectra orientation began to develop at take‐up speeds above 500 m/min. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 795–811, 2002     

Miscibility study of polymer blends composed of semirigid thermotropic liquid crystalline polycarbonate,poly(vinyl alcohol), and chitosan

Miscibility of binary and ternary polymer blends composed of thermotropic liquid crystalline polycarbonate (LCPC), poly(vinyl alcohol) (PVA), and chitosan was investigated by viscosity method, FTIR spectrum, and scanning electron microscope techniques. Effect of addition of chitosan as a compatibilizer on miscibility and morphology of binary LCPC/chitosan and PVA/chitosan and ternary LCPC/PVA/chitosan polymer blends was discussed. These measurements indicated that addition of chitosan into the blends of LCPC with PVA leads to an increase of miscibility and a formation of clear fibril structures on fractured surfaces, which are due to intermolecular hydrogen‐bonding interaction between LCPC, PVA, and chitosan chains. It was suggested that side‐chain hydroxy group of PVA and amino and hydroxy groups of chitosan play an important role in the formation of miscible phase and improvement of morphology in binary and ternary blends composed of LCPC, PVA, and chitosan. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1616–1622, 2004     

Thermal properties,structure and morphology of PEEK/thermotropic liquid crystalline polymer blends

The dynamic crystallization and subsequent melting behaviour of poly(aryl ether ether ketone), PEEK, and its blends with a thermotropic liquid crystalline polymer, Vectra^®, have been studied using differential scanning calorimetry, optical microscopy and wide‐angle and small‐angle X‐ray diffraction (WAXS and SAXS) techniques in a wide compositional range. Differences in crystallization rates and crystallinities were related to the structural and morphological characteristics of the blends measured by simultaneous real‐time WAXS and SAXS experiments using synchrotron radiation and optical microscopy. The crystallization process of PEEK in the blends takes place in the presence of the nematic phase of Vectra and leads to the formation of two different crystalline families. The addition of Vectra reduces the crystallization rate of PEEK, depending on composition, and more perfect crystals are formed. An increase in the long period of PEEK during heating was generally observed in the blends at all cooling rates. Copyright © 2003 Society of Chemical Industry     

Miscibility and mechanical properties of poly(ether imide)/poly(ether ether ketone)/liquid crystalline polymer ternary blends

This paper is concerned with a novel ternary blend composed of poly(ether imide) (PEI), poly(ether ether ketone) (PEEK) and a liquid crystalline polymer (LCP; HX4000, Du Pont). Different compositions were prepared by extrusion and injection moulding. Dynamic mechanical thermal analysis and the observation of the fracture surfaces, before and after annealing, allowed determination of the cold crystallization temperatures and miscibility behaviour of these systems. PEEK/PEI blends are known from previous studies to be miscible at all compositions. In this case it was observed that the PEEK/HX4000 blend was miscible up to 50 wt% HX4000 but partially miscible above this value. The PEI/HX4000 blends were found to be partially miscible in the whole concentration range. As a result, some ternary blend compositions exhibited only one phase, while others exhibited two phases. The measurement of the tensile properties showed that ternary blends with high modulus can be obtained at high LCP loadings, while compositions with high ultimate tensile strength can be obtained with high loadings of PEI or PEEK.     

Thermomechanical processing environment and morphology development of a thermotropic polymer liquid crystal

We have studied a longitudinal polymer liquid crystal consisting of poly(ethylene terephthalate) (PET) and p‐hydroxybenzoic acid, namely PET/0.6PHB, where 0.6 is the mole fraction of the second component. The material was injection molded with systematic variations of the melt and mold temperatures and injection flow rate using design of experiments based on a Taguchi orthogonal array. Thermomechanical environment defined by local melt temperatures and shear rates and stresses imposed during processing was estimated by computer simulations of the mold‐filling phase. The morphology of the moldings was characterized by optical and scanning electronic microscopy, wide‐ and small‐angle X‐ray scattering, and differential scanning calorimetry. An analysis of variance approach identified the significant processing variables and their contributions to variations of morphological parameters. The processing environment affects strongly the melt viscosity, and there is a strong thermo‐mechanical coupling. The result is a complex multilaminated and hierarchical microstructure, whose morphological features are very sensitive to the processing conditions. Relationships between local thermomechanical variables (rather than global ones) and the morphological parameters are established. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

FTi.r. studies of polymer blends containing the poly(hydroxy ether of bisphenol A) and poly(ε-caprolactone)

Fourier transform infra-red (FTi.r.) studies of the polymer blend system poly(hydroxy ether of bisphenol A) (phenoxy)-poly(ε-caprolactone) (PCL) are presented. These two polymers are miscible in the amorphous state and information concerning the presence and nature of intermolecular interactions between the two polymers has been gained. Specifically, direct evidence has been obtained for a hydrogen bonding interaction between the PCL carbonyl group and the phenoxy hydroxyl group. Significantly, the relative strength of this interaction is found to be weaker than the corresponding intermolecular hydrogen bonding interaction in pure phenoxy. In contrast, a cursoryFTi.r. study of phenoxy-poly(ethylene oxide) blends reveals that the intermolecular interaction occuring between these two polymeric components is stronger than that occuring in pure phenoxy. In addition, PCL is a crystallizable polymer and studies performed on the PCL-phenoxy blends at room temperature have led to further information on the state of order of PCL in these blends. The ramifications of these results are discussed.     

Effect of compatibilization on the oxygen‐barrier properties of poly(ethylene terephthalate)/poly(m‐xylylene adipamide) blends

The improvement of the oxygen‐barrier properties of poly(ethylene terephthalate) (PET) via blending with an aromatic polyamide [poly(m‐xylylene adipamide) (MXD6)] was studied. The compatibilization of the blends was attempted through the incorporation of small amounts of sodium 5‐sulfoisophthalate (SIPE) into the PET matrix. The possibility of a transamidation reaction between PET and MXD6 was eliminated by ¹³C‐NMR analysis of melt blends with 20 wt % MXD6. An examination of the blend morphology by atomic force microscopy revealed that SIPE effectively compatibilized the blends by reducing the MXD6 particle size. Thermal analysis showed that MXD6 had a nucleating effect on the crystallization of PET, whereas the crystallization of MXD6 was inhibited, especially in compatibilized blends. Blending 10 wt % MXD6 with PET had only a small effect on the oxygen permeability of the unoriented blend when it was measured at 43% relative humidity, as predicted by the Maxwell model. However, biaxially oriented films with 10 wt % MXD6 had significantly reduced oxygen permeability in comparison with PET. The permeability at 43% relative humidity was reduced by a factor of 3 in compatibilized blends. Biaxial orientation transformed spherical MXD6 domains into platelets oriented in the plane of the film. An enhanced barrier arose from the increased tortuosity of the diffusion pathway due to the high aspect ratio of MXD6 platelets. The aspect ratio was calculated from the macroscopic draw ratio and confirmed by atomic force microscopy. The reduction in permeability was satisfactorily described by the Nielsen model. The decrease in the oxygen permeability of biaxially oriented films was also achieved in bottle walls blown from blends of PET with MXD6. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1361–1370, 2005     

Crystallization kinetics of poly(ethylene terephthalate) with thermotropic liquid crystalline polymer blends

The isothermal and dynamic crystallization behaviors of polyethylene terephthalate (PET) blended with three types of liquid crystal polymers, i.e., PHB60–PET40, HBA73–HNA27, [(PHB60–PET40)–(HBA73–HNA27) 50 : 50], have been studied using differential scanning calorimetry (DSC). The kinetics were calculated using the slope of the crystallization versus time plot, the time for 50% reduced crystallinity, the time to attain maximum rate of crystallization, and the Avrami equation. All the liquid crystalline polymer reinforcements with 10 wt % added accelerated the rate of crystallization of PET; however, the order of the acceleration effect among the liquid crystalline polymers could not be defined from the isothermal crystallization kinetics. The order of the effect for liquid crystalline polymer on the crystallization of PET is as follows: (PHB60–PET40)–(HBA73–HNA27) (50 : 50); HBA73–HNA27; PHB60–PET40: This order forms the dynamic scan of the DSC measurements. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1383–1392, 1998     

氧化石墨烯改性热致液晶聚芳酯的结构性能研究

采用原位聚合法,通过熔融共聚制备了HBA/HNA-GO液晶聚酯复合材料。研究了不同添加量的氧化石墨烯对纳米复合材料形态、结构和性能的影响。通过对复合材料的研究发现,氧化石墨烯的添加不会破坏TLCP原有的微观结构,且能够提高HBA/HNA液晶聚酯的热稳定性,为进一步研制高性能热致液晶聚芳酯提供了一个很好的方向。     

Structure and mechanical properties of poly(trimethylene terephthalate)/poly(hydroxy ether of bisphenol A) blends

Compatible poly(trimethylene terephthalate) (PTT)/poly(hydroxy ether of bisphenol A) (Phenoxy) blends were obtained by direct injection molding throughout the composition range. Two amorphous phases with minor amounts of the other component were found in the blends. Reactions occurred in PTT‐rich blends. By comparing the miscibility level of these blends with that of other blends based on polyalkylene terephthalates, it is proposed that a miscibility limit delimited by a 3/1 methylene–carbonyl ratio in the polyalkylene terephthalate exits in these blends. The synergism in the Young's modulus of the blends is discussed as a consequence of the changes in the crystallinity of PTT, the specific volume and the orientation produced by blending. Ductility is approximately proportional to blend composition, indicating compatibility, and is attributed to the combined effects of a small particle size and a good adhesion level, the latter being a consequence of the partially miscible nature of the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3246–3254, 2006     

Blends of phenolphthalein poly(ether ether ketone) and a thermotropic liquid crystalline copolyester

Blends of phenolphthalein poly(ether ether ketone) (PEK-C) and a thermotropic liquid crystalline copolyester (LCP), poly[(1-phenylethyl-p-phenylene terephthalate)-co-(1-cumyl-p-phenylene terephthalate)], was prepared via melt mixing. The studies of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) indicate that the PEK-C/LCP blends display two glass transition temperatures which correspond to those of PEK-C- and LCP-rich phases, respectively. The PEK-C/LCP blends were judged to be partially miscible. Scanning electron microscopy (SEM) was employed to examine the morphology of the blends, and it was observed that all the PEK-C/LCP blends displayed a phase-separated structure. The interface between the PEK-C- and LCP-rich phases is poor. The Young's modulus of the PEK-C/LCP blends was found to increase with LCP content due to the high modulus of the LCP. However, the tensile strength and the elongation at break of the blends greatly decreases with increase of LCP content, owing to the poor interfacial adhesion. From the thermogravity analysis (TGA), it was observed that all the blends exhibited a two-step weight loss mechanism, and the thermal degradation onset temperature of the blends was lowered with the addition of LCP content. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1923–1931, 1998     

Improved thermal and mechanical properties of poly(butylene succinate) by polymer blending with a thermotropic liquid crystalline polyester

A novel polymer blending system consisting of poly(butylene succinate) (PBS) and a thermotropic liquid crystalline polyester [LCP: a poly(4‐hydroxybenzoate)‐based polymer] was investigated in the presence and absence of a polycarbodiimide (PCD) and/or 1,1′‐carbonyl biscaprolactam (CBC) as chain extenders. Although the LCP was immiscible with PBS, it formed elongated fibrous domains having an orientation in the flowing direction when an extensional flow was applied during the processing. Scanning electron micrograph (SEM) of the injection‐molded polymer blends supported the distribution of micro fibrils of LCP in the PBS matrix by which the efficient toughening was provided. These blend specimens showed highly improved mechanical properties along with retaining high dynamic storage‐moduli (E′) up to the melting temperature of PBS. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39952.     

New polymer to enhance the permanent memory effect of polymer dispersed liquid crystal films

Conventional polymer dispersed liquid crystals (PDLC) are devices with recognized applications. New PDLCs with permanent memory effect (PME) can be used as digital memory devices. The synthesis and characterization of a new monomer [pentaerythritoltetramethacrylate (PE4MA)] is here described. A PDLC was produced using the synthesized monomer (PE4MA) copolymerized with commercially available monomethacrylate oligomer poly(propyleneglycol) methacrylate (PPGMA) and 70% (w/w) liquid crystal (E7), showing 98% permanent memory effect, with 72% memory state contrast (MSC) and an electric field required to achieve 90% of the maximum transmittance (E₉₀) of 3 V µm^?1. The synthesized monomer (PE4MA) copolymerized with PPGMA seems to be a prospective material for preparation of PDLC with permanent memory effect with a view to application for digital memory devices based on write‐read‐erase cycles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43482.