Synthesis,characterization, and application of semi‐interpenetrating liquid crystalline polymer networks LCP/PS

Attempts to extend the IPN technology to liquid crystalline polymer (LCP) systems have been made in search for a new approach for enhancing the compatibility of liquid crystalline polymer with engineering thermoplastics. A new type of interpenetrating polymer network based on liquid crystalline polymer : semi‐interpenetrating liquid crystalline polymer network comprising liquid crystalline polymer PET/60PHB (LCP) and crosslinked polystyrene (PS) (for short: semi‐ILCPN LCP/PS) has been successfully prepared. The compatibility and thermal properties of the semi‐ILCPN LCP/PS with different amount of crosslinking agent were investigated by FTIR, SEM, DSC, and TGA, respectively. Furthermore, the possible application of the semi‐ILCPN LCP/PS as a new kind of compatibilizer in PPO/LCP blends was also studied and discussed. Well‐compatibilized PPO/LCP composites with considerably improved mechanical properties were obtained. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1141–1150, 2000     

In situ reactive compatibilized noryl/LCP blends

This article reveals that the already known improved properties of the thermoplastic–liquid crystalline polymer (LCP) blends can be further improved substantially over the corresponding noncompatibilized counterparts by using a reactive in situ type compatibilizer, the styrene–glycidyl methacrylate (SG) copolymer. This SG copolymer has been demonstrated in this article to be an effective reactive compatibilizer to improve the processability, heat deflection temperature, and mechanical properties of Noryl/LCP blends. The epoxy functional groups of the SG copolymer can react with the end groups of PPO (in Noryl) and LCP. The in situ-formed SG–g–LCP copolymer tends to reside along the interface of Noryl–LCP and reduces the interfacial tension during melt processing. The resultant LCP fibers in the Noryl matrix of the compatibilized blends have a higher aspect ratio because the fibers become finer, longer, and tend to form lamellate domains with a greater interphase contact area than those from the noncompatibilized blends. The compatibilized blends also improve the interphase adhesion between Noryl and LCP. The presence of ethyl triphenylphosphonium bromide catalyst promotes the grafting reaction to improve blend compatibilization. © 1995 John Wiley & Sons, Inc.     

In situ compatibilized SAN/LCP blends through reactive copolymers

Styrene–acrylonitrile–glycidyl methacrylate (SAG) copolymers with various contents of glycidyl methacrylate (GMA) were used to compatibilize the incompatible blends of styrene–acrylonitrile (SAN) and a liquid crystalline polymer (LCP). These SAG copolymers contain reactive glycidyl groups that are able to react with the carboxylic acid and/or hydroxyl end groups of the LCP to form the SAG‐g‐LCP copolymers during melt processing. The in situ–formed graft copolymers tend to reside along the interface to reduce the interfacial tension and to increase the interface adhesion. The morphologies of the SAN/LCP blends were examined by using scanning electron microscopy (SEM), where the compatibilized SAN/LCP blends were observed with greater numbers and finer fibrils than those of the corresponding uncompatibilized blends. The mechanical properties of the blends increased after compatibilization. The presence of a small amount (200 ppm) of ethyl triphenylphosphonium bromide (ETPB) catalyst further promotes the graft reaction and improves the compatibilization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3321–3332, 2001     

Ionization–liquid-crystalline polymer synergistically reinforced poly(ethylene terephthalate) due to interfacial compatibilization by ion–dipole interactions

To enhance the compatibility of poly(ethylene terephthalate) (PET)/liquid crystalline polymer (LCP) composite, thereby mechanically strengthening the PET matrix, an optimally compatibilized composite of chain-extended and -carboxylated PET ionomer and poly(4-hydroxybenzoic acid–ran–6-hydroxy-2-naphthoic acid) (HBA–HNA) was successfully prepared. Upon PET carboxylated chain extension with pyromellitic dianhydride and subsequent ionization with Zn(OH)₂, the compatibility of the composite was distinctly improved, as verified by the refined dispersed-phase morphology, increased number of refined HBA–HNA fibrils, reduced crystallinity, and improved complex viscosity. Compared with PET, the optimally compatibilized composite displayed a 70.1 and 148.7% increase in Young's modulus and tensile strength, respectively. Tentatively mechanistically, the interfacial interaction may change from weak hydrogen bonding to strong ion–dipole interactions due to the introduction of ionic groups, which remarkably boosts the interfacial compatibility, thereby achieving synergistic effects of the ionization and HBA–HNA inclusion to maximally strengthen PET. It seems that the synergistic ionization/LCP inclusion by a one-pot method establishes a promising preparation approach to commercial PET engineering resins.     

Rheological and physical properties of polyarylate/LCP blend systems

A polyarylate Unitika U-Polymer 100 (PAR) was melt blended with a thermotropic liquid crystalline polymer (LCP) Vectra A950, and the processingmorphology-properties relations were investigated. Inclusion of LCP slightly reduced T_g of PAR. The PAR/LCP blend with the LCP content higher than 50 wt% exhibited a noticeable yield stress, particularly in the vicinity of crystal-to-nematic transition temperature (T_cn). LCP lowered the blend viscosity above T_cn and seemed to play a role as processing aid. The tensile strength of the blends was increased with increasing spin draw ratio and level of LCP, and the spinning temperature influenced tensile strength. The relaxation behavior under dynamic shear and resultant blend morphology based on WAXD and SEM analyses are discussed as well.     

Injection molding of PC/PBT/LCP ternary in situ composite

A liquid crystalline polymer (LCP), Vectra B950, reinforced polycarbonate (PC) 60 wt%/polybutylene terephthalate (PBT) 40 wt% blend was studied using the injection molding process. Morphology and mechanical properties of ternary in situ LCP composites were investigated and compared with binary polycarbonate/Vectra B950 LCP composites. Good in situ fibrillation of LCP was observed in the direct injection-molded LCP composites. Preliminary results of this work indicate that addition of PBT improves skin-core distribution of LCP microfibrils in the matrix and also enhances adhesion between the matrix and Vectra B950, which contains terephthalic acid. The PC/PBT/LCP ternary system also exhibits lower viscosity than the PC/PBT blend and pure LCP. In a ternary system with 30 wt% of Vectra B950, tensile modulus and strength increase approximately threefold and twofold, respectively. The rule of mixtures (ROM) for continuous reinforcement can accurately represent the strengthening effects for the ternary LCP in situ composites. Generally, LCP reduces the ductility and impact strength of the thermoplastic blends; however, the relative loss is less in the ternary system than in the binary system.     

Compatibilization of poly(ethylene terephthalat)/liquid crystal polymer blends by means of bisphenol a polycarboate

A compatibilization method that consists of the addition of minor amounts of a commercial thermoplastic, which interacts or reacts with both the matrix and the dispersed liquid crystalline polymer (LCP) of thermoplastic/LCP blends, has been tested in the case of poly(ethylene terephthalate)/Vectra A950 (PET/VA) blends by means of the addition of bisphenol A polycarbonate (PC). The smaller particle size, rougher surface of the fibers and higher ductility of the PET/VA blends of a 30% of the PET substituted by PC clearly showed the suitability of PC as a compatibilizer. The moduli of elasticity of the compatibilized and uncompatibilized blends were similar. This was due to the less‐developed fibrillation of the compatibilized blends, a consequences of their smaller particle size and decreased matrix viscosity. These changes counteracted the effects of improved interfacial adhesion. The improved adhesion led to higher ductility and tensile and impact strengths in most of the compatibilized blends.     

Random orientation of in situ composites based on liquid‐crystalline polymers by compression moulding

In this study, randomly oriented in situ composites based on liquid‐crystalline polymers (LCPs) were prepared by thermal compression moulding. The LCP employed was a semi‐flexible liquid‐crystalline copolyesteramide with 30 mol% of p‐aminobenzoic acid (ABA) and 70 mol% of poly(ethylene terephthalate) (PET). The matrices were poly(butylene terephthalate) (PBT) and polyamide 66 (PA66). The rheological properties, compatibility and morphological structures of these in situ composites were investigated. The results showed that PA66‐LCP and PBT–LCP component pairs of the composites are miscible in the molten state, but partially compatible in the solid state. The ratios of viscosity, λ₁ = η_LCP/η_PA66 and λ₂ = η_LCP/η_PBT, are all greater than 1.0. However, the melt viscosity of the LCP/PBT and LCP/PA66 blend is much lower than that of PBT and PA66, and it decreases markedly with increasing LCP content. When the LCP/PA66 or LCP/PBT blends are compression moulded, the LCP/PA66 or LCP/PBT melts and flows easily due to their low viscosity, and the LCP phases in the melts deform easily along the flow directions, which are random. It leads to uniformly dispersed LCP micro‐fibres randomly orientation in the thermoplastic matrix due to the compatibility between the blending components. © 2003 Society of Chemical Industry     

Mechanical performance of ternary in situ polycarbonate/poly(acrylonitrile‐butadiene‐styrene)/liquid crystalline polymer composites

Ternary in situ polycarbonate (PC)/poly(acrylonitrile‐butadiene‐styrene) (ABS)/liquid crystalline polymer(LCP) composites were prepared by injection molding. The LCP used was a versatile Vectra A950, and the matrix of composite specimens was PC/ABS 60/40 by weight. Maleic anhydride (MA) copolymer and solid epoxy resin (bisphenol type‐A) were used as compatibilizers for these composites. The tensile, dynamic mechanical, impact, morphology, and thermal properties of the composites were studied. Tensile tests showed that the tensile strength of the PC/ABS/LCP composite in the longitudinal direction increased markedly with increasing LCP content. However, it decreased slowly with increasing LCP content in the transverse direction. The modulus of this composite in the longitudinal direction appeared to increase considerably with increasing LCP content, whereas the incorporation of LCP into PC/ABS blends had little effect on the modulus in the transverse direction. The impact tests revealed that the Izod impact strength of the composites in both longitudinal and transverse direction decreased with increasing LCP content up to 15 wt %; thereafter it increased slowly with increasing LCP. Dynamic mechanical analyses (DMA) and thermogravimetric measurements showed that the heat resistance and heat stability of the composites tended to increase with increasing LCP content. Scanning electron microscopy observation and DMA measurement indicated that the additions of epoxy and MA copolymer to PC/ABS matrix appeared to enhance the compatibility between the PC and ABS, and between the matrix and LCP. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2274–2282, 1999     

Impact-modified blends of compatibilized polyamide-6 with liquid crystalline copolyester

Compatibilized blends of polyamide-6 (PA6) and thermotropic liquid crystalline polymer (LCP) modified with various high-impact polypropylene (HIPP) contents were injection-molded. These blends were compatibilized with maleic anhydride-grafted polypropylene (MAP). The effects of impact modification on the morphology, impact, static, and dynamic mechanical properties were investigated. The results showed that the HIPP addition leads to an improvement of the Izod impact strength of the blends significantly while it reduced the tensile strength and stiffness properties. An attempt was made to correlate the structure of the PA6(MAP)/HIPP/LCP blends from the scanning electron microscopic observations with the measured mechanical properties. This work provides a way to produce a tough in situ composite. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1611–1619, 1998     

In‐situ reinforcement of PBT/ABS blends with liquid crystalline polymer

Ternary in‐situ poly(butylene terephthalate) (PBT)/poly(acrylonitrile‐butadienestyrene) (ABS)/liquid crystalline polymer(LCP) blends were prepared by injection molding. The LCP used was a versatile Vectra A950, and the matrix material was PBT/ABS 60/40 by weight. Maleic anhydride (MA) copolymer and solid epoxy resin (bisphenol type‐A) were used as compatibilizers for these blends. The tensile, dynamic mechanical, impact, morphology and thermal properties of the blends were studied. Tensile tests showed that the tensile stregth of PBT/ABS/LCP blend in the longitudinal direction increased markedly with increasing LCP content. However, it decreased sharply with increasing LCP content up to 5 wt%; thereafter it decreased slowly with increasing LCP content in the transverse direction. The modulus of this blend in the longitudinal direction appeared to increase considerably with increasing LCP content, whereas the incorporation of LCP into PBT/ABS blends had little effect on the modulus in the transverse direction. The impact tests revealed that the Izod impact strength of the blends in longitudinal direction decreased with increasing LCP content up to 10 wt%; thereafter it increased slowly with increasing LCP. Dynamic mechanical analyses (DMA) and thermogravimetric measurements showed that the heat resistance and heat stability of the blends tended to increase with increasing LCP content. SEM observation, DMA, and tensile measurement indicated that the additions of epoxy and MA copolymer to PBT/ABS matrix appeared to enhance the compatibility between PBT/ABS and LCP.     

Novel approach to fibrillation of LCP in an LCP/PP blend

A novel concept of improving shear‐induced fibrillation of liquid crystalline polymer (LCP) in LCP/thermoplastic blend systems was introduced. Silica fillers (SiO₂) were added to an LCP/polypropylene (PP) system to serve as a viscosity thickening agent and to improve the fibrillation of the LCP phase. The formation of LCP fibrils was found to enhance with the incorporation of 5–15 wt % of fillers. The presence of LCP fibrils improved the flow properties of the LCP/PP/SiO₂ composites. It was evident from the rheological and morphological studies that the addition of silica led to an increase of the aspect ratio of the LCP fibrils, which, in turn, should improve their effectiveness as reinforcements and/or toughening agents. Substantial improvement in LCP aspect ratio was achieved by the introduction of hydrophobic SiO₂ fillers in the PP/LCP blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2070–2078, 2002     

Crystallization kinetics of a PEEK/LCP blend

The crystallization kinetics of a polyetheretherketone (PEEK)/liquid crystalline polymer (LCP) blend was studied by using differential scanning calorimetry. Nonisothermal runnings were performed on heating and on cooling at different rates. Isothermal crystallization experiments at 315, 312, 310, and 307°C, from the melt state (380°C) were performed in order to calculate the Avrami parameters n and k and the fold surface free energy, σ_e. Polarized light optical micrographs were also obtained to confirm the Avrami predictions. It was observed that the LCP retarded the PEEK crystallization process and that the PEEK melting temperature decreased with the amount of LCP, but the LCP melting temperature increased with the amount of PEEK. Probably the PEEK improves the perfection of the LCP crystalline domains. A spherulitic morphology in pure PEEK and its blends was predicted by the Avrami analysis; however this morphology was only observed for pure PEEK and for the 80/20 composition. The other compositions presented a droplet and fibrillar-like morphology. The overall crystallization rate was observed to decrease with the crystallization temperature for all compositions. Finally, σ_e was found to decrease with the increase of LCP in the blends, having unrealistic negative values. Thus, calculations were made assuming σ_e constant at all compositions. It was observed that δ, the interfacial lateral free energy, decreased but still remained positive. It was concluded that in these blends neither σ_e nor σ could be considered constant. © 1995 John Wiley & Sons, Inc.     

The flexible PEI composites

The present study investigates the compatibilizing effect of polyphosphazene on the blends of poly(ether imide) (PEI) and thermotropic liquid crystalline polymer (Vectra‐B). FTIR study showed that there was a partial interaction or chemical reaction between the PEI and LCP in the presence of compatibilizer. Polyphosphazene is compatibilized with both PEI and LCP, which was evident from DMA results. From the X‐ray diffraction study, it has been observed that the crystalline structure of PEI–LCP blends was increased with the addition of compatibilizer. The thermal study of the composites has been studied by DTA/thermo gravimetric analyses (TGA). TGA thermograms showed an increase in decomposition temperature of PEI–LCP blends in the presence of compatibilizer. Measurement of the tensile properties showed an increase in the elongation as well as enhanced modulus and strength. From SEM micrographs of tensile fractured surfaces, the addition of compatibilizer to PEI–LCP blends was found to increase the adhesion between the matrix and the dispersed phase. POLYM. COMPOS., 27:533–538, 2006. © 2006 Society of Plastics Engineers     

Synthesis and characterization of semi-interpenetrating liquid crystalline polymer networks LCP/PAN

A new type of interpenetrating polymer network based on a liquid crystalline polymer: a semi-interpenetrating liquid crystalline polymer network comprising the liquid crystalline polymer (LCP) PET/60PHB and crosslinked polyacrylonitrile (PAN) (for short: semi-ILCPN LCP/PAN) was successfully prepared. The compatibility and thermal properties of the semi-ILCPNs with different amounts of the crosslinking agent were investigated by FTIR, SEM, DSC, and TGA. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 349–354, 1998     

Blends of a PPO–PS alloy with a liquid crystalline polymer

Blends of a PPO–PS alloy with a liquid crystalline polymer have been studied for their dynamic properties, rheology, mechanical properties, and morphology. This work is an extension of our previous work on PPO/LCP blends. The addition of the LCP to the PPO–PS alloy resulted in a marked reduction in the viscosity of the blends and increased processibility. The dynamic studies showed that the alloy is immiscible and incompatible with the LCP at all concentrations. The tensile properties of the blends showed a drastic increase with the increase in LCP concentration, thus indicating that the LCP acted as a reinforcing agent. The tensile strength, secant modulus, and impact strength of the PPO–PS/LCP blends were significantly higher than that of PPO/LCP blends. Morphology of the injection molded samples of the PPO–PS/LCP blends showed that the in situ formed fibrous LCP phase was preserved in the solidified form. A distinct skin–core morphology was also seen for the blends, particularly with low LCP concentrations. The improvement of the mechanical properties of the blends is attributed to these in situ fibers of LCP embedded in the PPO–PS matrix. The improvement in the properties of PPO–PS/LCP over PPO/LCP is also attributed to the addition of the PS which consolidates the matrix. © 1995 John Wiley & Sons, Inc.     

Mechanical and morphological study of polyphenylene sulfide/liquid crystalline polymer blends compatibilized with a maleic anhydride grafted copolymer

Blends of thermotropic liquid crystalline polymer (LCPA‐950), based on a copolyester of hydroxynapthoic acid and hydroxybenzoic acid with an engineering thermoplastic, poly(phenylene sulfide) (PPS), were prepared using a corotating twin‐screw extruder. Addition of a third component, a functionalized polypropylene (maleic anhydride grafted polypropylene, MA‐PP), that interact with the thermotropic liquid crystalline polymer (TLCP) facilitates the structural development of the TLCP phase by acting as a compatibilizer at the interface. Differential scanning calorimetry and dynamic mechanical thermal analysis results, however, show that there is an interaction between the polymers in the presence of compatibilizer. This means that MA‐PP can be used as a compatibilizer for the PPS/LCP in situ composite system. The viscosity of the compatibilized in situ composite was decreased by the compatibilizer, and this is mainly due to the fibrous structure of the LCP at the high shear rate. The mechanical properties of the ternary blends were increased when a proper amount of MA‐PP was added. This is attributed to fine fibril generation induced by the addition of MA‐PP. Morphological observations determined the significance of the third component in immiscible polymer blends, and an optimum amount of MA‐PP exists for the best mechanical performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Rheology and impact characteristics of compatibilized polypropylene-liquid crystalline polymer composites

Polypropylene-liquid crystalline polymer (PP/LCP) and maleic anhydride compatibilized PP/LCP blends were prepared using the extrusion technique followed by injection molding. The LCP employed was Vectra A950 which consists of 25 mol % of 2,6-hydroxynaphthoic acid and 75 mol % of p-hydroxybenzoic acid. The rheology, morphology, and impact behavior of compatibilized PP/LCP blends were investigated. The rheological measurements showed that the viscosity of LCP is significantly higher than that of the PP at 280°C. This implied that the viscosity ratio of the LCP to the polymer matrix is much larger than unity. Scanning electron microscopy (SEM) observations revealed that the LCP domains are dispersed mainly into elongated ellipsoids in the PP/LCP blends. However, fine fibrils with large aspect ratios were formed in the compatibilized PP/LCP blends containing LCP content ≥ 10 wt %. The development of fine fibrillar morphology in the compatibilized PP/LCP blends had a large influence on the mechanical properties. The Izod impact strength of the PP/LCP blends showed little dependence on the LCP concentrations. On the other hand, the impact strength of the compatibilized PP/LCP blends was dependent on the LCP concentrations. The correlation between the LCP fibrillar morphology and spherulitic structure with the impact properties of the compatibilized PP/LCP blends is discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 521–530, 1998     

Mechanical properties and morphology of LCP/ABS blends compatibilized with a styrene–maleic anhydride copolymer

A co‐polyester liquid crystalline polymer (LCP) was melt blended with an acrylonitrile–butadiene–styrene copolymer (ABS). LCP fibrils are formed and a distinct skin/core morphology is observed in the injection moulded samples. At higher LCP concentration (50 wt%), phase inversion occurs, where the dispersed LCP phase becomes a co‐continuous phase. While the tensile strength and Young's modulus remain unchanged with increasing LCP content up to 30 wt% LCP, a significant enhancement of the modulus at 50 wt% LCP is observed due to the formation of co‐continuous morphology. The blend modulus is lower than the values predicted by the rule of mixtures, suggesting a poor interface between the LCP droplets and ABS matrix. A copolymer of styrene and maleic anhydride (SMA) was added in the LCP/ABS blends during melt blending. It is observed that SMA has a compatibilizing effect on the blend system and an optimum SMA content exists for mechanical properties enhancement. SMA improves the interfacial adhesion, whereas excess of SMA reduces the LCP fibrillation. Copyright © 2003 Society of Chemical Industry     

Blends of PBT with rigid thermotropic LCP having flexible side groups: Comparison of their tensile properties with semirigid main-chain TLCP blends

Two new thermotropic liquid crystalline polymers (LCPs) were synthesized. One is a di-mesogenic LCP having a flexible hexamethylene spacer in the main chain, the other is a rigid-type main-chain LCP having alkoxy side groups on the terephthaloyl moiety of the polymer. Blends of LCP with poly(butylene) terephthalate were melt-spun at different LCP contents and different draw ratios to produce a monofilament. Maximum enhancement in the ultimate tensile strength was observed for the blends containing 5% LCP at any draw ratio, and decreased with further increase in LCP content. The initial modulus monotonically increased with increasing LCP content. The tensile properties of the rigid-type LCP blends were higher than those of the flexible main-chain LCP blends. © 1996 John Wiley & Sons, Inc.