Solidification behavior and recovery kinetics of liquid crystalline polymers

The supercooling behavior of three thermotropic liquid crystalline polymers (TLCP's), 60 mole% p-hydroxybenzoic acid and 40 mole% poly(ethyleneterephthalate), 60/40 PHB/PET, 80 mole% p-hydroxybenzoic acid and 20 mole% poly(ethyleneterephthalate), 80/20 PHB/PET and a copolyester of 73 mole% p-hydroxybenzoic acid and 27 mole% of 2-hydroxy-6-naphthoic acid, Vectra A900, was studied by means of both rheological and thermal methods. 60/40 PHB/PET and Vectra A900 exhibited a degree of supercooling as high as 80°C while there was only 20°C of supercooling for 80/20 PHB/PET. The degree of supercooling for the blends of 60/40 PHB/PET and 80/20 PHB/PET also decreased with the increase in 80/20 PHB/PET content. The increase in G′ as the temperature decreased was more gradual for 60/40 PHB/PET and Vectra A900 than that for 80/20 PHB/PET, which was beneficial from a processing point of view. The solidification of the LCP melt was attributed to both the crystallization and the freezing of the mesophase. The degree of crystallinity for all three TLCP's was very small, less than 5%, as measured by the DSC. It was found that both 60/40 PHB/PET and Vectra A900 showed an induction period of a few minutes during solidification while 80/20 PHB/PET solidified continuously at the test temperature. Therefore, 60/40 PHB/PET and Vectra A900 seem to be more suitable for use in processes such as blow molding and film blowing than 80/20 PHB/PET.     

Reactive blending of poly(ethylene terephthalate) with a liquid crystalline copolyester and polyhydroxyether

Poly(ethylene terephthalate) modified with a dianhydride (PET–anhydride) was melt‐blended with a liquid crystalline copolyester (Vectra A) in the presence of a small amount of a liquid crystalline polyhydroxyether. The mechanical properties of a blend consisting of PET–anhydride/Vectra A/polyhydroxyether were drastically improved compared to blends without polyhydroxyether or without anhydride. Melt‐spun fibers of PET–anhydride/Vectra A/polyhydroxyether in a 80/20/0.75 weight ratio displayed a much higher tensile modulus (17 GPa) and tensile strength (214 MPa) than did a 80/20 PET–anhydride/Vectra A blend (4 GPa and 60 MPa, respectively). A similar increase in modulus and strength was found for a 90/10/0.75 relative to a 90/10 blend. The tensile moduli of the blends can well be described by the Tsai–Halpin equation. A better fibril formation was observed, which was attributed to an improved viscosity ratio. Reactions between the various functional groups during melt processing were indicated by viscosity measurements. The polyhydroxyether may act as a reactive compatibilizer which improves the interfacial adhesion, chemically and/or physically. WAXD recordings of both blends showed a crystalline and highly oriented Vectra phase. The PET phase was unoriented and amorphous in a PET/Vectra blend and semicrystalline and weakly oriented in a PET/Vectra/polyhydroxyether blend. Postdrawing of the various blend fibers to λ = 4 increased the modulus by about 40% and the tensile strength by more than 100%, mainly through orientation of the PET phase. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1107–1123, 1999     

Morphology and mechanical properties of fibers from blends of a liquid crystalline polymer and poly(ethylene terephthalate)

The domain morphology and mechanical properties of fibers spun from blends of a thermotropic liquid crystalline polymer, Vectra A-900, and poly(ethylene terephthalate) (PET) have been studied across the entire composition range. The PET phase was removed by etching to reveal fibrillar LCP domains in the blends of all compositions. The 0.5μm fibril appeared to be the basic structural entity of the LCP domains. A primary effect of composition was the change from discontinuous fibrils when the composition was 35 and 60% by weight LCP to continuous fibrils when the composition was 85 and 96% LCP. This transition had major ramifications on the mechanical properties: the modulus increased abruptly between 60 and 85% LCP, and a change in the fracture mode from brittle fracture to a splitting mode was accompanied by an increase in fracture strength. Different models were required to describe the mechanical properties of the discontinuous and continuous fibril morphologies. Analytic models for short aligned fibers of Nielsen, and Kelly and Tyson were applicable when the LCP fibrils were discontinuous, while modulus and strength of blend fibers with continuous LCP fibrils were discribed by the rule of mixtures.     

Effective biosynthesis of poly(3‐hydoxy‐ butyrate‐co‐4‐hydroxybutyrate) with high 4‐hydroxybutyrate fractions by Wautersia eutropha in the presence of α‐amino acids

BACKGROUND: Biopolymers produced by microbes are in demand as their biodegradable and biocompatible properties make them suitable for disposable products and for potential use as biomaterials for medical applications. The effective microbial production of copolyesters of 3‐hydroxybutyrate (3HB) and 4‐hydroxybutyrate(4HB) with high molar fractions of 4HB unit by a wild‐type Wautersia eutropha H16 was investigated in culture media containing 4‐hydroxybutyric acid (4HBA) and different carbon substrates in the presence of various α‐amino acids. RESULTS: The addition of carbon sources such as glucose, fructose and acetic acid to the culture medium containing 4HBA in the presence of α‐amino acids resulted in the production of random poly(3HB‐co‐4HB) with compositions of up to 77 mol% 4HB unit, but the yields of copolyesters with 60–77 mol% 4HB units were less than 15 wt% of dried cell weights. In contrast, when carbon sources such as propionic acid and butyric acid were used as the co‐substrates of 4HBA in the presence of α‐amino acids, poly(3HB‐co‐4HB) copolyesters with compositions of 72–86 mol% 4HB were produced at maximally 47.2 wt% of dried cell weight (11.3 g L^?1) and the molar conversion yield of 4HBA to 4HB fraction in copolyesters was as high as 31.4 mol%. Further, poly(3HB‐co‐4HB) copolyesters with compositions of 93–96 mol% 4HB were isolated at up to 35.2 wt% of dried cell weights by fractionation of the above copolymers with chloroform/n‐hexane. CONCLUSION: The productivity of copolyesters with over 80 mol% 4HB fractions was as high as 0.146 g L^?1 h^?1 (3.51 g L^?1 for 24 h) by flask batch cultivation. Copyright © 2007 Society of Chemical Industry     

Effective microbial production of poly(4‐hydroxybutyrate) homopolymer by Ralstonia eutropha H16

The effective microbial production of copolyesters of 3‐hydroxybutyrate (3HB) and 4‐hydroxybutyrate (4HB) with high mole fractions of 4HB units by a wild‐type strain of Ralstonia eutropha H16 was investigated in culture solutions containing 4‐hydroxybutyric acid (4HBA) and various carbon substrates in the presence of a nitrogen source such as ammonium sulfate. The addition of glucose or acetic acid to the culture solution containing 4HBA in the presence of ammonium sulfate resulted in the production of random copolymers of P(3HB‐co‐4HB) with compositions of up to 82 mol% 4HB, but the yield of copolymers was less than 7 wt% of dried cell weights. In contrast, when n‐alkanoic acids such as propionic acid, butyric acid, valeric acid and hexanoic acid, being subject to β‐oxidation metabolism in the cell, were used as the co‐substrates of 4HBA in the presence of ammonium sulfate, a mixture of copolymers with two different 4HB compositions was produced, and copolyesters with compositions of 93–100 mol% 4HB were isolated from chloroform–n‐hexane insoluble fractions in the mixture of copolymers. Especially, when this wild‐type Ralstonia eutropha H16 was cultivated in a medium containing 4HBA (15 g litre⁻¹), propionic acid (5 g litre⁻¹) and ammonium sulfate (5 g litre⁻¹), namely C/N (mol/mol) = 10, the P(4HB) homopolymer was produced at maximally 34 wt% of dry cell weight (7.8 g litre⁻¹), and the conversion yield of 4HBA to P(4HB) homopolymer resulted in values as high as 21 mol%. © 1999 Society of Chemical Industry     

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     

Structures of liquid crystalline wholly aromatic copolyester films with different copolymer compositions

Films of wholly aromatic copolyester composed of 4-hydroxybenzoic acid (HBA) and 2-hydroxy-6-naphthoic acid (HNA) were prepared by a solution-casting method using a mixed solution of pentafluorophenol (PFP) and chloroform (weight ratio: PFP/chloroform = 3/7). Using five samples with different copolymer compositions (HBA/HNA [mol%] = 25/75, 40/60, 55/45, 62/38, 73/27), the effects of the copolymer composition on the fine structures of the films were investigated using thermal analyses, density measurements, X-ray diffraction methods, and tensile tests. The as-cast films obtained were shown to be trans-parent and highly amorphous in spite of changing the copolymer composition. When the films were heated above the T_g (100°C), cold crystallization first occurred during the heating process and they had melting points. The densities of the films increased with increasing annealing temperature throughout the cold crystallization. The elongation percentages of the as-cast films reached high values of 30–74% at room temperature, indicating their maximum of elongation at 55 mol% of HBA. © 1996 John Wiley & Sons, Inc.     

Study of the crystal structure of P(HBA/HNA)/PET blend fibers

The crystal structure of p‐hydroxybenzoate/2‐hydroxy‐6‐naphthoic acid copolyester [P(HBA/HNA)]/poly(ethylene terephthalate) (PET) blend (ACPET) fiber was studied with wide‐angle X‐ray diffraction and differential scanning calorimetry. The results showed that crystallites of P(HBA/HNA) and PET were formed in ACPET fibers; that is, some crystallites of ACPET fiber were composed of PET chains, and others were composed of P(HBA/HNA) chains. The thermal behaviors of the crystals of each component in the blend fiber were different from those of each corresponding pure component. For the fibers heat‐treated at 300 and 350°C, the degree of supercooling of P(HBA/HNA) segments in the blend fibers was the same as that of P(HBA/HNA) fiber, but the degree of supercooling of PET in the blend fibers was distinctly higher than that of pure PET fibers. Evidently, the aforementioned changes were attributable to the blending of PET with P(HBA/HNA). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 394–400, 2002     

Revisit the crystallization mechanism of vectra,™ a liquid crystal polymer

We have studied isothermal transition kinetics and crystallization mechanisms of the Hoechst Celanese liquid crystal polymer Vectra™ A‐950 using a differential scanning calorimetry. This material is a random copolymer with a composition made of 73 mol %/27 mol % of HBA (1,4‐dihydroxybenzoic acid)/HNA (2,6‐dihydroxynaphthoic acid). When comparing our results to previous work on 75/25 HBA/HNA, we found some similarities as well as dissimilarities. In the case of similarities, both polymers show two types of transition processes in the low‐temperature region (below 495 K). One is a fast process, which can be regarded as liquid crystal transition, and is characterized by a heat of fusion that does not vary significantly with annealing time. The other transition is a slow process related to crystal perfection and shows increases in the heat of transition and the transition temperature with increasing annealing time. However, the apparently slight difference in polymer composition also leads to a few surprising results. For example, previous work on 75/25 HBA/HNA two transition peaks (slow and fast processes) were observed after annealing it at 505 K, while in the current work only one transition peak in the case of 73/27 HBA/HNA was observed. In addition, based on the relationship between heat of fusion and annealing time, the LCP made from 73/27 HBA/HNA may perfect faster (in the time scale we study); hence, its posttreatment processes may be accomplished more efficiently than that of 75/25 HBA/HNA. This result also suggests that the former may have a better sequence or a better matching of molecular dimensions for crystallization than that of the latter. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1139–1150, 1999     

Separation of hydroxybenzoic acid isomers using the molecular imprinting technique

Molecular imprinting polymers (MIPs) for salicylic acid (SA), 3‐hydroxybenzoic acid (3HBA), and 4‐hydroxybenzoic acid (4HBA) were synthesized using styrene and 4‐vinylpyridine (4‐VPy) as functional monomer and divinylbenzene (DVB) as crosslinker. The adsorption characteristics of hydroxybenzoic acid (HBA) isomers on each MIP were investigated. The materials used for the polymerization of each 3HBA and 4HBA‐MIPs were adsorbed relatively well. This verifies that the MIPs that can adsorb template selectively were synthesized. However, SA‐MIP had no molecular imprinting effect. SA has intramolecular hydrogen bond and it is difficult to adsorb on recognition site of SA‐MIP, because its structure differs from that of recognition site of SA‐MIP. It indicates that SA‐MIP had no recognition effect. 1,2,3,4‐Tetrahydro‐1‐naphthol (THN)‐MIP was synthesized, which is similar to SA with intramolecular hydrogen bond. SA was separated selectively using THN‐MIP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Thermal and morphological properties of thermotropic liquid‐crystalline copolyesters containing poly(ethylene terephthalate), 4‐hydroxyphenylacetic acid and main‐chain rigid aromatic units

Thermotropic liquid‐crystalline polymers (TLCPs) have aroused considerable interest due to their attractive properties as high‐performance materials. Significant research attention has been devoted to investigating the relationship among monomer structures, syntheses and end‐use properties of TLCPs. The study reported here concerns the preparation, characterization and melt spinning of novel copolyesters containing two different flexible units together with two different aromatic units in the polymer chains. A range of copolyesters based on p‐hydroxybenzoic acid (p‐HBA), m‐hydroxybenzoic acid, p‐hydroxyphenylacetic acid and poly(ethylene terephthalate) were synthesized. The liquid crystallinity, thermal properties and degrees of crystallinity of these copolyesters were investigated using hot‐stage polarized light microscopy, differential scanning calorimetry, thermogravimetry and wide‐angle X‐ray diffraction. Copolyester fibres were characterized using scanning electron microscopy. The copolyesters were melt‐processable, thermally stable and could be processed above their melting temperatures without degradation. The degree of crystal structure was found to depend upon the content of p‐HBA. The fibres prepared showed that polymer chains had a well‐developed fibrillar structure. Novel TLCPs containing flexible units in the main chain were synthesized and characterized. Copolyesters containing p‐HBA units ranging from 55 to 70 mol% exhibited phase‐separated liquid‐crystalline morphology, appropriate melting temperatures and high thermal stability for melt processing. Copyright © 2010 Society of Chemical Industry     

Melt‐electrospinning of poly(ethylene terephthalate) and polyalirate

Rodlike polymer samples were made from three kinds of poly(ethylene terephthalate) (PET) pellets with different intrinsic viscosities (IV), and from polyalirate (Vectra) pellets. PET and Vectra fibers were produced using a melt‐electrospinning system equipped with a CO₂‐laser melting device from these rodlike samples. The effects of IV value and laser output power on the fiber diameter of PET were investigated. Furthermore, the effect of the laser output power on the fiber diameter of Vectra was investigated. The crystal orientation of these produced fibers was also investigated by X‐ray photographs. The following conclusions were reached: (i) the diameter of PET fiber decreases with increasing laser output power; (ii) the minimum average diameter of PET fibers is scarcely influenced by the value of IV; (iii) the electrospun PET fibers show isotropic crystal orientation; (iv) fibers having an average fiber diameter smaller than 1 μm cannot be obtained from PET and Vectra using the system developed; and (v) preferred liquid crystal orientation can be seen in electrospun Vectra fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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.     

Synthesis and Characterization of Novel Thermotropic Aromatic-Aliphatic Biodegradable Copolyesters Containing D,L-Lactic acid (LA), Poly(butylene terephthalate) (PBT) and Biomesogenic Units

In this study, the copolyesters based on 4-hydroxybenzoic acid (HBA) and vanillic acid (VA), lactic acid (LA) and poly(butylene terephthalate) (PBT) were synthesized via melt polymerization and fully characterized by various measurements. The influences of content of HBA and VA units on thermal behavior, structure and degree of crystallinity of copolyesters were discussed in more detail. It was found that the copolymerization of aliphatic and aromatic units together could make the best use of advantages of the respective polyesters. Moreover, the copolyesters with more than 40 mol% of HBA and VA units could show liquid crystallinity in broad temperature range.     

Structure and properties of blend fibers from poly(ethylene terephthalate) and liquid crystalline polymer

The structure and properties of the as-spun fibers of poly(ethylene terephthalate) (PET) blends with a thermotropic liquid crystalline polymer (LCP), Vectra A900, were studied in detail. The DSC results indicate that the LCP component may act as a nucleating agent promoting the crystallization of the PET matrix from the glassy state but which inhibits its crystallization from the melt due to the existence of an LCP supercooled mesophase. The effect of the drawdown ratio on the orientation of the as-spun blend fibers is highly composition-dependent, which is mainly associated with the formation of LCP fibrils during melt spinning. The modulus of the as-spun blend fibers has a significant increase as the content of LCP reaches 10%, while the tensile strength has a slightly decreasing tendency. The mechanical properties of the as-spun blend fibers could be well improved by heat treatment because of a striking increase in the crystallinity of the PET matrix. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 217–224, 1997     

Viscoelastic properties of a 60 mol% para-hydroxybenzoic acid/40 mol% poly(ethylene terephthalate) liquid crystalline copolyester. I: Effect of temperature history

In this paper, the rheology of a 60 mol% para-hydroxybenzoic acid (PHB)/40 mol% poly(ethylene terephthalate) (PET) copolyester (herein referred to as PHB60/PET40) produced by Unitika Co., Japan, was investigated using viscoelastic property temperature sweeps. In addition to the large-scale hysteresis (super-cooling) of viscoelastic properties that has also been seen with other PHB-based materials, in which it is possible for several PHB linkages to occur side by side along the polymer backbone (most notably the PHB60/PET40 polymer produced by Tennessee Eastman), smaller-scale viscoelastic transitions, one present in heating, and believed to be associated with the partial isotropization of liquid crystalline material, and the other apparent on cooling, occurring at a lower temperature than the first and thought to be associated with the opposite process, were observed. When overall mol% PHB composition along individual chains is considered, the well-defined appearance of the additional smaller-scale rheological transitions seen here is believed to be due to a unimodal composition distribution, rather than a bimodal distribution of which there is increasing evidence in the Tennessee Eastman materials. This difference is believed to be caused by differences in the preparation technique used for the Unitika version of the polymer.     

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.     

Copolyesters of poly(ethylene terephthalate), hydroquinone diacetate,and terephthalic acid: A simple rate model for catalyzed synthesis in melt

Transesterification reactions between poly(ethylene terephthalate) (PET), hydroquinone diacetate (HQDA), and terephthalic acid (TA), were conducted via the melt polymerization route with the objective of analyzing the copolyesterification kinetics of a phase separated system. At first homopolymerization of HQDA and TA were conducted at 50 mol % composition of each monomer. Then the polymerization kinetics of four compositions [PET 30/70 (HQDA + TA), PET 40/60 (HQDA + TA), PET 50/50 (HQDA + TA), PET 60/40 (HQDA + TA) with 30 : 35 : 35, 40 : 30 : 30, 50 : 25 : 25, and 60 : 20 : 20 mol % PET, HQDA, and TA] were investigated. The following assumptions were made to make kinetic analysis tractable. HQDA and TA combine to form acetic acid and higher oligomers. The oligomer subsequently adds on to the PET chain to give a copolymer of PET/HQDA/TA, the product of interest. The reaction between PET, HQDA, and TA proceeds in a heter-ogeneous two-phase system consisting of PET-rich and PET-poor regions. The reaction sequence is HQDA and TA react to form a dimer and subsequently the dimer is added onto the PET chain. This reaction sequence is assumed to be valid for the PET-rich and PET-poor phases. Both these reactions were assumed to be second order with respect to the reactants. Reactions wherein the dimer reacts with HQDA or TA to form acetic acid exist, but the probabilities of these processes are small with respect to the main reaction postulated above, thus maintaining the overall mass balance. Moles of acetic acid found experimentally were computed using a standard procedure. The rate constant k under the conditions of phase separation was determined. The rate constant in the presence of PET was higher than that observed in the HQDA and TA reaction. An Arrhenius plot revealed that the catalyst plays a marginal role. Microscopic analysis revealed that the HQDA and TA polymer were nonmelting while copolyesters PET 30/70 (HQDA + TA) to PET 60/40 (HQDA + TA) melted and were liquid crystalline. © 1996 John Wiley & Sons, Inc.     

The effect of blending temperature,composition, and shear rate on PET/Vectra A900 LCP blend viscosity and morphology

The rheological and morphological properties of several melt-blended compositions of poly(ethylene terephthalate) (PET) and Vectra A900 liquid crystalline polyester were investigated, using blending temperature, composition, and shear rate as variables. Rheological behavior was determined at several shear rates on an Instron capillary rheometer at 300°C, and three-dimensional surface plots of the results were prepared, detailing the effect on melt viscosity of changes in the variables. Scanning electron microscopy was used to examine the internal morphology of selected samples. In the preparation of melt blends containing an isotropic and anisotropic polymer, blending temperature and composition both influence the resulting morphology. These effects are accentuated during extrusion of the blends at low shear rates and diminished at high shear rates.     

Effect of thermotropic copolyesteramide on the properties of polyamide‐66/liquid crystalline copolyester composites

Liquid crystalline copolyester‐polyamide 66 (LCPES/PA66) composites compatibilized by liquid crystalline copolyesteramide (LCPEA) were prepared by injection molding. The LCPES employed was a commercial copolyester, Vectra A950, and the LCPES was a semiflexible thermotropic copolyesteramides based on 30 mol% of p‐amino benzoic acid (ABA) and 70 mol% of poly(ethylene terephthalate) (PET). Thermal analysis, mechanical characterization, and morphological investigations were conducted on the blends. The dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) tests showed that LCPEA is an effective compatibilizer for the LCPES/PA66 composites. The mechanical measurements showed that the stiffness, tensile strength and Izod impact strength of the in‐situ composites are improved by adding LCPEA because of the compatibilization and reinforcement to LCPES/PA66 composites. However, the properties improvement vanished when LCP content reached 10 wt%. The drop weight dart impact test was also applied to analyze the impact fracture characteristics of these composites. The results showed that the maximum impact force (F_max), crack initiation and propagation energy all improved with the addition of a small percent of LCPEA. From these results, it appeared that LCPEA prolongs the time for crack initiation and propagation. It also increases the energies for crack initiation and propagation, thereby leading to toughening of the LCPES/PA66 in‐situ composites. Finally, the correlation between the mechanical properties and morphology of the composites is discussed.