Polyesters based on hydroxybenzoic acid,hydroquinone, sebacic acid,and suberic acid Molecular design towards broad nematic range

Abstract

To achieve a thermotropic liquid crystalline polymer with a relatively low melting temperature and a broad mesophase range, a series of polyesters based on hydroxybenzoic acid (HBA), hydroquinone (HQ), sebacic acid (SEA), and suberic acid (SUA) have been designed and synthesised. The molecular design was based on two concepts. First, the flexible segment of SUA is shorter than that of SEA. Replacement of SEA with SUA units would lead to an increase in the chain rigidity and hence the nematic to isotropic transition temperature. Second, since SEA and SUA have similar reactivity, the partial replacement of SEA with SUA units would randomise the structure and thus cause depression of melting points. DSC shows that the melting temperatures of some HBA/HQ/SEA/SUA polymers are indeed lower than the corresponding HBA/HQ/SEA polymer. Liquid crystallinity of the polymers was examined using polarised light microscopy. This verified that the clearing point of the HBA/HQ/SEA/SUA polymers increases as the SUA concentration increases. At a HBA/HQ/SEA/SUA molar ratio of 60:40:20:20, the crystallites melt completely at ~200°C, while the clearing point is still well above 300°C. This liquid crystalline polyester has great potential to act as a processing aid for conventional thermoplastics with moderate processing temperature windows.     

Effect of interfacial interaction on rheological behavior of blends of a semiflexible liquid‐crystalline polyester and polycarbonate

A liquid‐crystalline polyester based on hydroxybenzoic acid, hydroquinone, sebacic acid, and suberic acid (named as BQSESU) was melt blended with polycarbonate (PC) at the BQSESU concentration of 2 wt %. It was found that the extent of viscosity reduction induced by the addition of BQSESU depends on the compounding temperature and the relation between them is not monotonic. The lowest viscosity was achieved by blending at 280°C. GPC measurements indicate that molecular weight reduction induced by the compounding is not a major contributor to the viscosity reduction. SEM study shows that when compounded at 280°C the blend is partially miscible with particle size at the submicron level. At the same time a large T_g depression was observed, which indicates strong interactions between the flexible segments of BQSESU and PC in the interfacial regions. The lowest viscosity achieved by blending at 280°C is thus proposed as an interfacial phenomenon. When compounded at 265°C, BQSESU particle size is larger, which gives a small interfacial area and hence less viscosity reduction. When compounded at 300°C a nearly miscible morphology was achieved, which also leads to less viscosity reduction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3051–3058, 2003     

In situ composites from blends of polycarbonate and a thermotropic liquid‐crystalline polymer: The influence of the processing temperature on the rheology,morphology, and mechanical properties of injection‐molded microcomposites

This work was aimed at understanding how the injection‐molding temperature affected the final mechanical properties of in situ composite materials based on polycarbonate (PC) reinforced with a liquid‐crystalline polymer (LCP). To that end, the LCP was a copolyester, called Vectra A950 (VA), made of 73 mol % 4‐hydroxybenzoic acid and 27 mol % 6‐hydroxy‐2 naphthoic acid. The injection‐molded PC/VA composites were produced with loadings of 5, 10, and 20 wt % VA at three different processing barrel temperatures (280, 290, and 300°C). When the composite was processed at barrel temperatures of 280 and 290°C, VA provided reinforcement to PC. The resulting injection‐molded structure had a distinct skin–core morphology with unoriented VA in the core. At these barrel temperatures, the viscosity of VA was lower than that of PC. However, when they were processed at 300°C, the VA domains were dispersed mainly in spherical droplets in the PC/VA composites and thus were unable to reinforce the material. The rheological measurements showed that now the viscosity of VA was higher than that of PC at 300°C. This structure development during the injection molding of these composites was manifested in the mechanical properties. The tensile modulus and tensile strength of the PC/VA composites were dependent on the processing temperature and on the VA concentrations. The modulus was maximum in the PC/VA blend with 20 wt % VA processed at 290°C. The Izod impact strength of the composites tended to markedly decrease with increasing VA content. The magnitude of the loss modulus decreased with increasing VA content at a given processing temperature. This was attributed to the anisotropic reinforcement of VA. Similarly, as the VA content increased, the modulus and thus the reinforcing effect were improved comparatively with the processing temperature increasing from 280 to 290°C; this, however, dropped in the case of composites processed at 300°C, at which the modulus anisotropy was reduced. Dynamic oscillatory shear measurements revealed that the viscoelastic properties, that is, the shear storage modulus and shear loss modulus, improved with decreasing processing temperatures and increasing VA contents in the composites. Also, the viscoelastic melt behavior (shear storage modulus and shear loss modulus) indicated that the addition of VA changed the distribution of the longer relaxation times of PC in the PC/VA composites. Thus, the injection‐molding processing temperature played a vital role in optimizing the morphology‐dependent mechanical properties of the polymer/LCP composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Rheology and morphology of some thermoplastic blends with a liquid crystalline copolyester

Liquid crystalline polymers (LCPs) are known for their high performance properties. However, owing to their high cost, research efforts are much oriented to their use as reinforcements for different thermoplastics. In this study, we investigated the morphology, mechanical and dynamic rheological properties of blends of a 60/40 para hydroxybenzoic acid–ethylene terephthalate copolyester LCP (PHB/PET) with poly(butylene terephthalate) (PBT), poly(hexamethylene terphthalate) (PHMT), and polycarbonate (PC). Addition of up to 30 wt% of LCP to the different thermoplastics was performed in a Haake Rheomix mixer at 300°C. The dynamic rheological properties of the blends showed significant changes upon the addition of LCP, but no improvement in the mechanical properties was observed. The rheological properties of the blends below the nematic transition temperature of the LCP (210°C) were similar to those of solid filled thermoplastics. At 270°C, at which the LCP is in the nematic phase, the viscosity of LCP blends with PC blends decreased, whereas that obtained with PBT blends was increased. This is interpreted as being due to the differences in viscosity and interfacial tension between the components and to a possible reaction between the LCP and the thermoplastics.     

Single‐Point Determination of Intrinsic Viscosity of Semirigid Thermotropic Copolyesters in Phenol/1,1,2,2‐Tetrachloroethane

A series of semirigid thermotropic copolyesters with different compositions were prepared from p‐hydroxybenzoic acid (HBA), hydroquinone (HQ), terephthalic acid (TPA) and poly(ethylene terephthalate) (PET) by acidolysis reaction and following polycondensation. Fourteen procedures of calculation of the intrinsic viscosities from a single viscosity measurement for polymer solutions, including three proposed ones, have been applied for the copolyesters in phenol/1,1,2,2‐tetrachloroethane (60/40, v/v) at 30°C. It is found that various forms of the Huggins and Kraemer equations, used singly or in a combined form, yield intrinsic viscosities in good agreement with those extrapolated values obtained in the usual manner from multipoint viscosity measurements over a wide range of concentrations.     

Studies on a terephthalic acid and dihydroxydiphenyl sulfone liquid crystalline copolymer and its composites with different thermoplastics

A liquid crystalline polymer (LCP) was synthesized by an interfacial polycondensation reaction at room temperature from terephthaloyl chloride and p,p′-dihydroxydiphenyl sulfone. The LCP synthesized was so stable and molecularly rigid that it did not show any phase transition until it degraded at about 320°C. Composites of the LCP with polycarbonate (PC), polystyrene (PS), and sulfonated polystyrene (SPS) were formed by compression molding at a temperature at which the thermoplastic matrix was in the melt state. They were thermally analyzed by differential scanning calorimetry. Tensile specimens were cut from the compression-molded plates, and mechanical tests were performed. The morphology of the material systems was studied by performing scanning electron microscopy analysis on cryogenically fractured specimens. For LCP/PS and LCP/SPS systems, a sharp two-phase morphology was formed, which suggested poor interfacial adhesion. The tensile strength of both systems decreased with LCP addition. The LCP/PC system also revealed a two-phase morphology; however, the interfaces between the LCP domains and the PC matrix were not so well defined, showing better interfacial adhesion than the two previous systems studied. Stronger bonding between the LCP and PC resulted in a significant improvement in the mechanical behavior of PC by LCP addition. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 645–652, 1997     

Flexible all‐aromatic polyesterimide films with high glass transition temperatures

A series all‐aromatic poly(esterimide)s with different molar ratios of N‐(3′‐hydroxyphenyl)‐trimellitimide (IM) and 4‐hydroxybenzoic acid (HBA) (IM/HBA = 0.3/0.7 and 0.7/0.3) was prepared with the aim to design flexible high T_g films. Melt‐pressed films, either from high molecular weight polymer or cured phenylethynyl precursor oligomers, exhibit T_gs in the range of 200 °C to 242 °C and are brittle. After a thermal stretching procedure, the films became remarkably flexible and very easy to handle. In addition, the thermally stretched 3‐IM/7‐HBA and 7‐IM/3‐HBA films show tensile strengths of 108 MPa and 169 MPa, respectively. Thermal treatment increased the T_g of 3‐IM/7‐HBA from 205 °C to 248 °C, whereas the T_g of 7‐IM/3‐HBA increased from 230 °C to 260 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 133, 44774.     

Wood‐fiber/high‐density‐polyethylene composites: Compounding process

The compounding process directly influenced the compounding quality of wood–polymer blends and finally affected the interfacial bonding strength and flexural modulus of the resultant composites. With 50 wt % wood fiber, the optimum compounding parameters for the wood‐fiber/high‐density‐polyethylene blends at 60 rpm were a temperature of 180°C and a mixing time of 10 min for the one‐step process with a rotor mixer. The optimum compounding conditions at 90 rpm were a temperature of 165°C and a mixing time of 10 min. Therefore, a short compounding time, appropriate mixing temperatures, and a moderate rotation speed improved the compounding quality of the modified blends and the dynamic mechanical properties of the resultant composites. The melt torque and blend temperature followed a polynomial relationship with the loading ratio of the wood fiber. The highest melt torque and blend temperature were obtained with 50% wood fiber. The coupling treatment was effective for improving the compatibility and adhesion at the interface. The two‐step process was better than the one‐step process because the coupling agents were more evenly distributed at the interface with the two‐step process. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2570–2578, 2004     

Interfacial properties of polycarbonate/liquid‐crystal polymer and polystyrene/high‐impact polystyrene polymer pairs under shear deformation

We developed an energy model derived from the first principle for multilayer configurations to enhance our understanding of the interfacial property between two polymers under shear deformation. We carried out specific experiments satisfying the boundary and loading conditions of the model to obtain the energy dissipation factor (β), which characterized and quantified the interfacial property. Two polymer pairs, the miscible system polystyrene (PS)/high‐impact polystyrene (HIPS) and the immiscible system polycarbonate (PC)/liquid‐crystal polymer (LCP), were investigated. As expected, β was zero for PS/HIPS, reflecting the strong interaction at the PS/HIPS interface. For PC/LCP, the value of β could be significant, and its behavior was complex; it reflected the thermal sensitivity and thermal history effect of the PC/LCP interface. A positive value of β also indicated the possibility of slip at the interface and provided an explanation for the negative deviation from the rule of mixture. This complex behavior of the interface was attributed to the changes in the phases and microstructure of LCPs and, therefore, the LCP/PC interface as thermal cycling was carried out in the melting/nematic range of LCPs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 258–269, 2003     

The effect of composition on thermal,mechanical, and morphological properties of thermotropic liquid crystalline polyester with alkyl side-group and polycarbonate blends

A thermotropic liquid crystalline polymer (LCP) with an alkyl side-group was synthesized. Blends of the LCP with polycarbonate (PC) were prepared by coprecipitatton from a common solvent. The rheological behavior of the LCP/PC blends was found to be very different from that of PC, and significant viscosity reductions were observed in the temperature range of 200–230°C. Blends of different LCP compositions were extruded with different draw ratio from a capillary rheometer. The ultimate tensile strength showed a maximum at a 10 wt% LCP composition in the blends. It decreased for compositions greater the 10 wt% LCP, whereas the initial modulus increased with increasing LCP content. The morphology of the blends was found to be affected by their compositions. Scanning electron microscopy (SEM) studies revealed finely dispersed spherical LCP domains in the PC matrix. The SEM micrographs also showed a poor adhesion between the two phases.     

Rheology of phase separated blends of two thermotropic liquid crystalline copolyesters

The melt rheology of phase separated blends of two thermotropic liquid crystalline polymers (LCPs) have been studied. The two components are a random copolyesters consisting of 73 mol% 4-hydrobenzoic acid (HBA) and 27 mol% 6-hydroxy-2-napthoic acid (Vectra A900 of Hoechst Celanese Corp.) and a poly(ethylene terephalate-co-4-oxybenzoate) containing 60 mol% HBA units (PET/60HBA of Eastman Kodak Corp.). Most striking is the effect of adding 10% PET/60HBA to Vectra A900: The viscosity at 290°C drops by a factor of 4 and the terminal zone of the relaxation time spectrum is shifted to much shorter times. This is an interesting effect that could be used for LCP processing even if its origin is not yet understood. Differential scanning calorimetry measurements support the hypothesis that the blend is phase separated and that no transestification reaction occurs during the experiments.     

Electrorheological effect of liquid crystalline polymers

Large increases in shear stress upon application of a 2.0 kV/mm electric field were observed in homogeneous fluids composed of polysiloxane-based liquid crystalline polymers (LCPs) in dimethyl silicone at a shear rate of 200 s^?1. The increase was largest (about 3,000 Pa at 50°C) with LCP consisting of a polysiloxane bearing mesogenic groups as side chains. With LCP having the mesogenic groups within the main chain, the maximum increase was about 1,300 Pa at 90°C. It was about 400 Pa at 30°C with LCP having the mesogenic groups at both ends only (biterminal), and several Pa at 30°C with LCP having the mesogenic group at one end only (monoterminal). The increases were smaller with mesogenic groups of lower positive dielectric anisotropy in the side chain LCP. The side chain, biterminal, and monoterminal LCPs exhibited Newtonian flow in the electric field and shear stress yield at low shear rates in its absence. The complex dynamic modulus and viscosity of the side chain LCP in the electric field showed no dependence on strain at deformation displacements approaching 5°, but in its absence were generally strain-dependent, and suggest the strong electrorheological effect of these homogeneous LCP fluids is related to a flexible-chain linkage between their crystalline domains. © 1995 John Wiley & Sons, Inc.     

Self‐reinforcing elastomer composites based on ethylene–propylene–diene monomer rubber and liquid‐crystalline polymer

In this study, the prime factor determining the size, shape, and distribution of liquid‐crystalline polymer (LCP) was the viscosity ratio at the processing conditions. The fiber‐forming capacity of the LCP depended on the viscosity of the ethylene–propylene–diene monomer rubber (EPDM). With increasing LCP content, the tensile and tear strengths did not increase, perhaps because of incompatibility between the EPDM and LCP. The hardness increased because of the hard mesogenic groups in the LCP. The percentage swelling decreased as the LCP content increased. With increasing LCP content, processability became easier because of a lower melt viscosity. The scorch time increased at higher LCP levels. A higher percentage crystallinity was observed with increasing LCP content. Scanning electron microscopy clearly showed the fiber phase formation, which was two‐dimensionally isotropic in nature, confirming fiber formation even in a shear field. The addition of LCP improved the thermal stability. The onset degradation temperatures shifted to higher values with increasing LCP content. Dynamic mechanical thermal analysis revealed that with the addition of LCP, the mechanical damping increased at its lower level. High‐temperature processing increased the effective amorphous zone. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 711–718, 2004     

Factors influencing microstructure formation in polyblends containing liquid crystalline polymers

Four isotropic polymers, poly(butylene terephthalate) (PBT), polycarbonate (PC), polyethersulfone (PES) and polysulfone (PSU), were blended by extrusion with a thermotropic liquid crystalline polymer (LCP) at different temperatures. The morphology of extrudates was observed by means of scanning electron microscopy and the intrinsic aspect ratio of LCP fibrils and particles separated from matrix resin was measured with an image analysis. Special attention was paid to the LCP fibrillation in these four matrices in a wide temperature range from 270 to 360°C and the internal relations among the effects of processing parameters, such as viscosity ratio, extrusion temperature, and LCP concentration. The results show that the viscosity ratio of the dispersed LCP phase to the continuous phase is a decisive factor determining the formation of LCP fibrils, but its effect closely relates with the LCP content. In the range of viscosity ratios investigated, 0.004 to 6.9, and lower LCP content of 10%, significant fibrillation took place only at viscosity ratios below 0.01. It is predicted that the upper limit of the viscosity ratio for LCP fibrillation will increase with increasing LCP content. A comparison of the morphologies of LCP/PES blends with different LCP concentrations reveals that the LCP phase becomes continuous at a concentration of less than 50%, and high LCP content does not always favor the formation of long and uniform LCP fibrils. The extrusion temperature has a marked effect on the size of the minor LCP domains. For fibril forming systems, the percentage of LCP fibrils with larger aspect ratios increases with increasing extrusion temperatures. All these results are explained by the combined role of deformation and coalescence of the LCP disperesed phase in the blend.     

Significant enhancement of thermal conductivity in graphite/polyester composite via interfacial π–π interaction

Interfacial thermal resistance between matrix and filler is one of the most serious factors hindering heat transfer in composites. Here, a type of liquid crystalline polyester (LCP) containing phenyl pendant groups was intended to blend with pristine graphite by interfacial interaction. The intensity at 26.6° of the wide angle X‐ray diffraction pattern which exceeded that of pristine graphite indicated the existence of a strong interfacial π–π interaction. Both DSC and XRD tests showed that the ordered structure of the LCP matrix is directly affected by the mass fraction of graphite, indicating the interfacial interaction between LCP and graphite. By increasing the content of graphite, the thermal diffusivity showed a sharp increment by 1004%. The maximum thermal conductivity of the composite reached 28.613 W m^?1 K^?1, which was seven times that of traditional thermoplastic blended with graphite. Compared with the data calculated using effective medium theory, interfacial interaction plays a significant role in enhancing the thermal conductivity of the composites. Furthermore, the maximum tensile strength of this series of composites reached 13.3 MPa and the maximum Young's modulus reached 1067 MPa, exhibiting a potential guideline for further applications in flexible electronics. © 2019 Society of Chemical Industry     

Crystallinity of poly(arylene ether nitrile) copolymers containing hydroquinone and bisphenol A segments

The hydroquinone (HQ) and bisphenol A (BPA) type poly(arylene ether nitrile) (PEN) (HQ/BPA‐PEN) were synthesized through nucleophilic aromatic substitution polymerization from HQ, BPA, and 2,6‐dichlorobenzonitrile (DCBN). The prepared copolymers were characterized by intrinsic viscosity, Fourier transform infrared (FTIR), and dynamic rheological analysis. The properties of resultant copolymers were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and mechanical testing. The results showed that the PEN copolymers exhibited crystallization performance with excellent thermal and mechanical properties. HQ/BPA‐PEN10 was made into films by solution‐casting process and then were treated at different temperatures (200, 260, 280, 300, 310, and 320 °C) for different times (1, 2, 3, 4, and 5 h) to investigate the crystallinity. Results showed that when isothermal treatment temperature is 310 °C and isothermal treating time is 4 h, HQ/BPA‐PEN10 showed best properties. At this condition, the melting enthalpy, crystallinity, tensile strength, and elongation at break of the sample is 17.7 J/g, 14.11%, 132.9 MPa, and 6.1%, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46412.     

Rheological hybrid effect in dually filled polycarbonate melt containing liquid crystalline polymer

Polycarbonate (PC)/liquid crystalline polymer (LCP) blends dually filled with glass fiber and nano‐SiO₂ were prepared by melt blending, with the use of a commercial Vectra A130 as the source of LCP and glass fiber. In these dually filled PC/LCP melts, rheological hybrid effect occurred, confirmed by the melt viscosity of the quadruple polymer blends decreased with increasing nano‐silica loading, influenced by the minor LCP phase in the blend. The drastic viscosity reduction closely correlates with the deformation and fibrillation of LCP droplets in the system. The LCP fibrillation was controlled jointly by the thermodynamic and hydrodynamic driving forces. Finally, the dually filled PC/LCP melt had decreased viscosity lower than those of pure PC, silica‐filled PC, and PC/Vectra A130 blends, and furthermore had decreased glass fiber breakage, shown by larger average aspect ratio than that in PC/Vectra A130 blends. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Effect of a filler on the rheological and mechanical properties of the liquid‐crystalline polyester–poly(methyl methacrylate) blends

The rheological and mechanical properties of the blends of liquid‐crystalline polyester (LCP) and poly(methyl methacrylate) (PMMA) filled with aluminum borate whiskers have been studied. It was established the combined action of reinforcing LCP and filler onto the property of PMMA matrix leads to marked reinforcing of PMMA. At 10% of filler and 30% of LCP, the tensile strength of PMMA increases by 30% and elasticity modulus by 110%, the processability being no worse. The viscosity of the blend PMMA + 30% LCP + 10% filler practically is the same as the PMMA melt viscosity at 220°C. With increasing concentration of LCP up to 30%, the filler effect in binary matrix becomes more essential. The possible reason is the preferential adsorption of LCP at the filler interface (surface segregation) and additional ordering of LCP near the surface, possible, due to additional stretching of nematic phase in the convergent flow zone. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 993–999, 2000     

Shear rate dependence of viscosity and first normal stress difference of LCP/PET blends at solid and molten states of LCP

The liquid crystalline polymer (LCP) and polyethylene terephthalate (PET) were blended in an elastic melt extruder to make samples having 20, 40, 60, 80, and 100 wt % of LCP. Morphology of these samples was studied using scanning electron microscopy. The steady state shear viscosity (η), dynamic complex viscosity (η*) and first normal stress difference (N₁) were evaluated and compared at two temperatures: 265°C, at which LCP was in solid state, and 285°C, at which LCP was in molten state. The PET was in molten state at both the temperatures. The shear viscosity of the studied blends displayed its dependence on composition and shear rate. A maxima was observed in viscosity versus composition plot corresponding to 80/20 LCP/PET blend. The N₁ increased with LCP loading in PET and with the increased asymmetry of LCP droplets. The N₁ also varied with the shear stress in two stages; the first stage demonstrated elastic deformation, whereas second stage displayed dominant plastic deformation of LCP droplets. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2212–2218, 2007     

Rheology,morphology and properties of LCP/Nylon 66 composite fibers

The rheology, morphology and properties of the composite systems of LCP, Vectra A^TM 950 and Nylon 66 were investigated. The viscocity ratio of LCP and matrix has strong influence on their morphology. For LCP blends, the viscosity ratio of LCP is a critical factor in determining the blend morphology. The optical micrographs show that the good fibrillation can be achieved when the viscocity of the dispersed LCP phase is less than that of the Nylon 66 matrix at 310°C. The dispersed LCP domains tend to be spherical or cluster‐like when the viscosity ratio of the disperesed LCP phase and the Nylon 66 matrix is more than 1 at 280°C. The scanning electron microscopy (SEM) and optical micrograph observations show that Nylon 66 is immiscible with LCP, and there are two distinct phases in the blends. The morphology of LCP phase changes with the composition. LCP exhibits a fine fibril dispersed phase in the Nylon 66 matrix in the low LCP concentration. With an increase in LCP concentration, the morphology of LCP phase is changed form a fine fibril dispersed phase to a perfectly aligned continuous fiber reinforced phase in the rich LCP concentration. The tensile moduli increase with LCP concentration, especially in the rich LCP concentration. The tensile strengths increase with LCP concentration only when LCP concentration is above 40 wt%. Compared to the pure Nylon 66 fiber, the 40 wt% LCP composite sample shows a 982.1% increase in tensile modulus and a 123.3% increase in tensile strength. The mechanical properties of composite fibers are below the rule of mixtures if the LCP concentration is low, but above the rule of mixtures if the LCP concentration is high.