Rheological and mechanical properties of polycarbonate–liquid-crystalline polymer blends with controlled chemical reactions

Chemical reactions can occur during the melt blending of polymers containing an ester group because ester groups are usually unstable at high temperatures; this instability generally deteriorates the mechanical properties of blends. Here, effects of chemical reactions on the rheological and mechanical properties of polycarbonate (PC)/liquid-crystalline polymer (LCP) blends are carefully investigated to determine a method for minimizing such undesirable impacts. For comparison, a physical blend, in which chemical reactions were minimized, was prepared at 300 °C in a twin-screw extruder. Both shear viscosity and complex viscosities of reactive blends were lower than those of physical blends, being almost proportional to [M_w ]^3.4 as a result of depolymerization and transesterification. Because of the enhanced miscibility, the tensile modulus of reactive blends increased compared with that of physical blend, according to the increase in the degree of incorporation (DI). It was also possible to increase tensile modulus if triester was added to the reactive blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2799–2807, 2001     

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.     

A study on blends of liquid crystalline copolyesters with polycarbonate. II. Transesterification control

The inhibited and catalyzed ester exchange (transesterification) during melt blending of poly(bisphenol-A carbonate) (PC) and liquid crystalline poly(oxybenzoate-co-ethylene terephthalate) (POB–PET 40/60; P46) was investigated with differential scanning calorimetry. It was found that the ester exchange between P46 and PC was effectively inhibited for a 20% P46 blend at 240°C, as further confirmed by nuclear magnetic spectroscopy. When the blending temperature and P46 concentration increased, only the transesterification between the PET segment in P46 and PC took place under inhibition. The morphology of the blends was analyzed with scanning electron microscopy and displayed a disconnected interface between P46 and PC under inhibition. Conversely, the transesterification took place between the POB segment in P46 and PC when a catalyst was added. © 1996 John Wiley & Sons, Inc.     

Transesterification effects on miscibility polycarbonate/poly(butylene adipate-<Emphasis Type="Italic">co</Emphasis>-terephthalate) blends

The effects of transesterification on the miscibility of polycarbonate (PC)/poly(butylenes adipate-co-terephthalate) (PBAT) blends were investigated. The PC/PBAT blends were prepared with a twin-screw extruder, and then annealed at 260 °C for 5 h to trigger the transesterification reaction. ¹H NMR, FT-IR, and WAXD results indicated that transesterification in the annealed PC/PBAT blends took place and led to the formation of a random copolymer structure. Because the copolymer serves as a compatibilizer, the PC/PBAT blends showed improved miscibility, as confirmed by FE-SEM and DMA analyses. The compatible morphology achieved through transesterification ultimately increased the thermal stability of the PC/PBAT blends. We could thus conclude that transesterification in PC/PBAT blends forms a random copolymer which plays an important role as a compatibilizer and consequently improves the miscibility as well as the thermal properties of the blends.     

Rheological and physical properties of in situ composite based on liquid crystalline polymer and poly(ethylene 2,6‐naphthalate) blends

The in situ composites based on poly(ethylene 2,6‐naphthalate) (PEN) and liquid crystalline polymer (LCP) were investigated in terms of thermal, rheological, and mechanical properties, and morphology. Inclusion of LCP enhanced the crystallization rate and tensile modulus of the PEN matrix, although it decreased the tensile strength in the PEN‐rich phase. The orientation effect of this blend system was composition and spin draw ratio dependent, which was examined by Instron tensile test. Further, the addition of dibutyltindilaurate (DBTDL) as a reaction catalyst was found to increase the viscosity of the blends, enhance its adhesion between the dispersed LCP phases and matrix, and led to an increase of mechanical properties of two immiscible blends. Hence DBTDL is helpful in producing a reactive compatibilizer by reactive extrusion at the interface of this LCP reinforced polyester blend system. The optimum catalyst amount turned out to be about 500 ppm, when the reaction proceeded in the 75/25 PEN/LCP blend system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2448–2456, 1999     

Reactive extrusion of in-situ composite based on PET and LCP blends

The “in-situ” compatibilization for a PET/LCP blend via transesterification reactions in a twin-screw extruder having a very short residence time is investigated through thermal, rheological, and mechanical studies. Inclusion of a small amount of liquid crystalline polymer (LCP) enhanced the crystallization rate of the poly(ethylene terephthalate) (PET) matrix. It acted as a nucleating agent. LCP lowered the blend viscosity above T_cn (crystalline-nematic transition temperature), working as a processing aid. However, the addition of dibutyltindilaurate (DBTDL) as a reaction catalyst was found to increase the viscosity of the blends, diminish the size of the dispersed phase, enhance its adhesion with the matrix, and lead to an increase of mechanical properties of two immiscible phases. Hence DBTDL is helpful in producing a reactive compatibilizer by reactive extrusion at the interface of this polyester blend system. The optimum catalyst amount turned out to be about 500 ppm when the reaction proceeds in 90/10 PET/LCP polyester blend systems. Its effect on the mechanical properties is discussed in detail. The structural change of reactive blend was identified by H¹ NMR and wide angle X-ray diffraction patterns.     

Thermal and mechanical properties of injection molded liquid crystalline polymer/amorphous polymer blends

Injection molded samples of binary blends of Vectra (LCP) and the three amorphous polymers polyethersulfone (PES), polycarbonate (PC), and aromatic poly(ester carbonate) (APEC) have been subjected to morphological and rheological characterization, and coefficients of linear thermal expansion and Young's moduli have been determined. The Young's modulus of the PES/LCP blends exhibited a near lower-bound behavior that could be predicted by the one-adjustable-parameter equations of Halpin-Tsai (ζ = 0.18) and Takayanaga (b = 0.23), whereas the coefficients of linear thermal expansion followed the Takayanaga equation with a value of b = 0.50. The chain orientation of the LCP component was essentially constant in all PES/LCP blends with a Herman's orientation parameter of 0.39 ± 0.03. Transesterification reactions led to randomization of the constituents of the PC/LCP and APEC/LCP blends. The effect was more pronounced in the PC/LCP blends. The introduction of the LCP into the PC/LCP blends led to no reduction in melt viscosity and no self-reinforcement. APEC/LCP exhibited self-reinforcement in blends with a content greater than 27 vol% LCP, and especially the blend with 67 vol% LCP. The self-reinforcement was caused by the presence of an oriented LCP phase, confirmed by X-ray diffraction, and by improved interfacial bonding, presumably resulting from the transesterification reactions occurring at the phase boundaries.     

Viscosity‐reducing effects of two semiflexible liquid‐crystalline polyesters with different chain rigidities in a matrix of polycarbonate

Two liquid‐crystalline polyesters (LCPs) with different chain rigidities were synthesized and melt‐blended with polycarbonate (PC) at an LCP concentration of 2 wt %. The first LCP (LCP1) was based on hydroxybenzoic acid (HBA), hydroquinone (HQ), sebacic acid (SEA), and suberic acid (SUA) and contained a relatively high concentration of flexible units (SEA and SUA). The other one (LCP2) was based on HBA, hydroxynaphthoic acid, HQ, and SEA and contained a lower concentration of flexible units. LCP2 had a much lower melting point, a higher clearing temperature, and a lower shear viscosity than LCP1. The blending was carried out at 265, 280, and 300°C for both systems. The extent of the viscosity reduction induced by the addition of LCP1 depended on the compounding temperature, and the lowest viscosity was achieved with blending at 280°C. This was attributed to the large interfacial area and interactions between the flexible segments of LCP1 and PC chains at the interface. For PC/LCP2, the viscosity reduction was not significantly dependent on the compounding temperature, and when it was compounded at 280°C, its viscosity was significantly higher than that of PC/LCP1 at high shear rates, even though LCP2 had lower viscosity. A scanning electron microscopy study revealed that, with compounding at 265 and 280°C, LCP2 was poorly dispersed in the PC matrix in comparison with LCP1, and the glass‐transition‐temperature depression caused by the addition of LCP2 was relatively small. This indicated that interfacial interactions in PC/LCP2 were weaker, thereby explaining their different rheological behavior in comparison with PC/LCP1. With compounding at 300°C, the compatibility of both systems improved because of transesterification reactions, but this did not lead to a lower viscosity because of the lack of physical interfacial interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 960–969, 2004     

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.     

Morphology and rheological properties of polypropylene/reactive elastomer blends

The relation of morphology to the linear viscoelastic properties for polymer blends consisting of an inert polypropylene and an elastomeric dispersed phase, made of two miscible copolymers, EVA and EMA, was investigated. The rheological properties of the elastomeric phase were modified by crosslinking in presence of an organometallic catalyst. The activation energy for the transesterification reaction taking place between EVA and EMA has been determined by following the increases of the complex viscosity with time and temperature. The Palierne model has been used to describe the linear viscoelastic behavior of the blends, and to estimate the interfacial tension between the immiscible components. The model was shown to describe relatively well the linear viscoelastic properties of reactive and nonreactive blends containing 30% or less elastomer. In parallel, the morphology of reactive and nonreactive blends (i.e. without catalyst in the elastomeric phase), before and after rheological experiments, has been determined using scanning electron microscopy. The size of the dispersed elastomeric particles for reactive blends prepared using an internal mixer was found to be, in most cases, much smaller than that for nonreactive blends.     

Rheological Properties of PC/EVA Blend Compatibilized with the Transesterification

The rheological properties of PC/EVA blends had been investigated by a Haake torque rheometer. The effects of blending temperature, a polycarbonate and a catalyst on the rheological properties of PC/EVA blends were discussed. The transesterification between PC and EVA, catalyzed by dibutyl tin oxide (DBTO), were investigated by differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). The results indicate that the chain break of PC or EVA can be accelerated by DBTO, which induces the equilibrium torque of PC or EVA to decrease as the DBTO content increases. But for the PC/EVA blend, as the blending temperature of increases, the increase of viscosity induced by the generation of the PC-EVA copolymer exceeds the decrease of viscosity induced by the chain break of PC and EVA. Therefore, the equilibrium torque of the PC/EVA blend with varying DBTO content is higher than that of uncatalyzed PC/EVA blend at the higher temperature, 250°C, compared with the lower temperature, 210°C. The content of PC in the blend influences the probability of transesterification and the generation of PC-EVA copolymer. The PC/EVA blend with 50 wt. %PC has the highest torque compared with the other blends.     

A study on blends of liquid crystalline copolyesters with polycarbonate. I. Compatibility by transesterification

Blends of poly(bisphenol-A carbonate) (PC) and synthesized liquid crystalline poly(oxybenzoate-co-ethylene terephthalate 40/60) (P46) were prepared through meltmixing in a Brabender mixer. The miscibility of the blends at different compositions and blending time was investigated with differential scanning calorimetry. The corresponding morphology of the blends was analyzed with scanning electron microscopy. It was found that for blends containing more than 20% P46 and mixed at 250°C or above the transesterification between PC and P46 took place. This transesterification was confirmed at a blend containing 40% P46 by nuclear magnetic resonance spectroscopy. The transesterification happened first between PC and the ester in the poly(ethylene terephthalate) (PET) block and then between PC and the ester in the polyoxybenzoate (POB) block. At 260°C and after 60 min' blending, the blend containing 30% P46 became an almost compatible system for appearing of a single glass transition temperature. This is also verified by the disappearing of P46 droplets in the PC matrix in the micrographs' observation. After 60 min' of blending, the compatibility of the system can be greatly improved even for the blend containing 40% P46 mixed at 260°C by the micrograph's observation. © 1995 John Wiley & Sons, Inc.     

Rheology and transesterification between polycarbonate and polyesters

Rheological behavior of polycarbonate (PC)–polyester blends is studied. The miscibility and rheological behavior are discussed. Effect of catalyst, tetra‐n‐butyl orthotitanate on the transesterification reactions for a [60 (PC):40 (PET or PBT)] blend is studied rheologically. The blends were mixed for different spans of time for rheological study. The blends are analyzed on the basis of the mechanism suggested by other researchers. As the mixing time is increased, the blends show decrease in viscosity. Random copolymers also are amorphous in nature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2039–2047, 2007     

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     

Investigation of exchange reactions and rheological response of reactive blends of poly(trimethylene terephthalate) and phenoxy resin

BACKGROUND: Reactive melt blends of poly(trimethylene terephthalate) (PTT) with a phenoxy resin (Ph) are some of the most interesting classes of reactive blends in which different kinds of exchange reactions can occur. This work is devoted to the study of these reactions and their effect on the rheological and morphological properties of the blends. RESULTS: The occurrence of transesterification reactions was confirmed by ¹H NMR analysis. Scanning electron microscopy observations confirmed that all the blends, except PTT/Ph 90/10 (w/w), which exhibits a droplet‐in‐matrix morphology, are homogeneous. At the beginning of transesterification, the melt viscosity of the blends is more influenced by molar mass increasing reactions than by molar mass decreasing ones. After extension of the reaction time and increase in temperature the molar mass reducing reactions become predominant, which results in a reduction of the complex viscosities. CONCLUSION: This work provides new data on the transesterification reactions involving the secondary hydroxyl groups of phenoxy. The properties of PTT/Ph blends are strongly determined by the transesterification reactions, which on the one hand results in the formation of PTT‐grafted phenoxy chains and on the other hand a decrease in the molar mass of non‐bonded PTT. These reactions exert a distinct compatibilizing effect between the blend components. Copyright © 2008 Society of Chemical Industry     

Influence of catalyst on transesterification between poly(lactic acid) and polycarbonate under flow field

This paper investigated the effect of catalyst on transesterification and transesterification mechanism between poly(lactic acid) (PLA) and polycarbonate (PC) under flow field. Three catalysts (zinc borate, titanium pigment and tetrabutyl titanate) were evaluated. It is found that transesterification reaction can take place without any catalyst, while three catalysts can all promote the transesterification reaction between poly(lactic acid) and polycarbonate to a greater extent. ¹H nuclear magnetic resonance spectroscopy, gel permeation chromatography and dynamic mechanical analysis revealed that structures of copolymers are not identical in the blends with and without catalyst. For pure blend, most of copolymers have relatively high molecular weight with low PC content, which implies that transesterification reaction most likely happens only once between a PLA chain and a PC chain during mixing process, and only a small amount of multiple reactions happen. However, for the catalyst systems, catalysts induce much more multiple reactions accompanying with the reducing molecular weight in copolymers and increasing PC content. Moreover, it is found that the catalysts not only affect the chain compositions of the product copolymers, but also influence the amount of polymers involved in the reaction. Tetrabutyl titanate is found to be the most effective catalyst in this study where the amount of reacted polycarbonate is more than 4 times of that in pure blend. It is found that PLA segments in copolymer are easily aligned on the interface due to its relatively high Deborah number, which increases the probability of its contact with more PC chains. Although the flow effect on the alignment of chain segment is similar in blends with and without catalysts, the acceleration of reaction due to catalyst makes it possible for multiple reactions. The match of the reaction time and contact time of chain segment of PC and PLA at interfaces is then of key importance in the interfacial transesterification reaction. The effect of flow field on the interfacial reaction is then not only from the interfacial update, but also from the change of chain conformation near the interface.     

Structure–property relationship in fibers spun from poly(ethylene terephthalate) and liquid crystalline polymer blends. II. Effect of spinning temperature on fiber properties

A series of fibers based on neat poly(ethylene terephthalate) (PET) and PET/10% liquid crystalline polymer (LCP) blends were spun at various temperatures, ranging from 250 to 310°C, and the effect of spinning temperature on properties was studied. Improved tensile strengths and higher moduli of hot-drawn fibers were obtained with fibers spun at and above 300°C, which was explained by increased transesterification and the randomized structure of the PET/LCP blends. © 1995 John Wiley & Sons, Inc.     

Study on ester–amide exchange reactions between Nylon 1010 and Ethylene‐vinyl acetate rubber

Reactive processing is a useful method to improve the compatibility of immiscible polymer blends. Nylon 1010/Ethylene‐vinyl acetate rubber (EVM) blends were prepared via melt blending at 240°C and tetrabutyl titanate (Ti(OBu)₄) was used as a catalyst. Ester–amide exchange reactions were proven to take place between Nylon and EVM during the shear processing. Melt flow index, Fourier transform infrared spectroscopy, and proton nuclear magnetic resonance spectra were used to study the reactions. It was demonstrated that tuning the shear rate could control the properties and reaction extent of Nylon 1010/EVM/Ti(OBu)₄ blends. The results revealed that the reactions were promoted by high shear rate. Tensile strength of the blends increased from 4.5 to 11.4 MPa when the shear rate increased from 20 to 80 rpm. Meanwhile, scanning electron microscopy was adopted to study the morphology of the reactive blends. It was found that the morphology of the blends was changed from sea‐island structures to co‐continuous structures while increasing the shear rate from 20 to 100 rpm. Dynamic mechanical analysis confirmed that high‐shear processing was found to promote the compatibility of the blends. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40064.     

Blends of Poly(hydroxybutyrate) and Poly(ethylene succinate) Prepared in the Presence of Samarium

Blends of the commercial biodegradable polymer poly(hydroxybutyrate) (PHB) with the oligomeric polyester poly(ethylene succinate) (PES) were prepared by melt processing in the presence of Sm(acac)₃. The occurrence of transesterification reactions during blend processing using the samarium catalyst was investigated. ¹H NMR analyses showed no evidence of transreactions, even using high content of catalyst (4 wt%), long reaction times and high temperatures (200°C). Under the drastic reaction conditions employed, chain degradation characterized by a significant decrease in the molecular weight (MW) of PHB has taken place. PHB/PES blends form immiscible systems in which the PHB crystallizes as large spherulites, but its crystallization is significantly influenced by the presence of PES, which does not crystallize at conditions in which the poly(hydroxyalkanoate) is crystallized.     

Processing and composition dependence of the structure and mechanical properties of polycarbonate/ultrax blends

Polycarbonate (PC)/Ultrax blends were obtained by injection molding changing both the Ultrax content and the injection temperature, speed and pressure. The change of injection speed or pressure did not lead to significant change of morphology or properties. An injection temperature of 300°C allowed some reaction to take place between the components and the presence of some reacted Ultrax in the PC-rich phase, but the mainly spherical morphology obtained lead to poor mechanical properties. At a lower injection temperature of 280°C, however, reactions were almost not detected, but fibrillar structures were produced, mainly because of the higher matrix viscosity. This gave rise to important increases not only in modulus and tensile strength but also in flexure properties and creep dimensional stability.