Poly(ethylene terephthalate)/polyarylate blends: Influence of interchange reactions on the melting behavior of poly(ethylene terephthalate)

The influence of the interchange reactions of poly(ethylene terephthalate) (PET)/polyarylate (PAr) blends on the melting behavior of isothermally crystallized PET has been studied. PET shows three melting endotherms in the pure state and also when mixed with PAr. These endotherms are explained in terms of primary and secondary crystallization processes as well as recrystallization during the calorimetric scan. It is also shown that interchange reactions hinder the crystallization processes of PET.     

Blends of poly(ethylene terephthalate) and a polyarylate before and after transesterification

Blends of poly(ethylene terephthalate) (PET) and a copolyester of bisphenol A–terephthaloylisophthaloyl (PAr) (2:1:1) have been studied both before and after transesterification. The physical blends exhibit phase separation in their amorphous states: a pure PET phase and a mixed PAr-rich phase. In spite of this phase separation, PET crystallinity in blends, normalized to PET fraction, surprisingly goes through a maximum at 25% PAr content. The transesterfied copolymers are noncrystallizable and exhibit a single T_g between those of starting polymers, PET and PAr.     

Ternary polymer mixtures: Polyarylate/phenoxy/poly(butylene terephthalate)

The intended objective of this work was to bring together two immiscible polymers, polyarylate (PAr) and Phenoxy [poly(hydroxy ether of bisphenol-A)], preparing ternary mixtures with a third component, poly(butylene terephthalate) (PBT). Experimental results showed that ternary mixtures containing 30% or more PBT gave single glass transition temperatures by DSC. Moreover, the PBT melting point depended on the composition of the mixtures. These results, which could be indicative of the existence of a single amorphous phase in these blends, have been discussed. Nevertheless, results must be considered with caution, given the peculiarities of the T_g–composition diagrams for the miscible pairs PAr/PBT and Phenoxy/PBT. Hypothetic interchange reactions during melting have been found to be unimportant.     

Transesterification reaction of polyarylate and copolyester (PETG) blends

Transesterification reactions between polyarylate (PAr) and a copolyester (PETG) have been investigated by proton nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FTIR), and differential scanning calorimetry. Blends of PAr and PETG were prepared by melt mixing and solution-casting with weight fractions of PAr in the blends varying from 0.90 to 0.10. The PETG is a copolyester containing ethylene-1,4-cyclohexylene dimethylene terephthalate. From the thermal analysis of the PAr/PETG melt blends, a single glass transition temperature is observed, which indicates a miscibility between the PAr and PETG. The benzene insoluble fraction of the PAr/PETG (50/50) melt blends and solution-cast blends were characterized using NMR and FTIR. The results of NMR and FTIR support the conclusion that transesterification reactions between the PAr and PETG occurred under the melt blending conditions applied.     

Application of styrene‐acrylonitrile random copolymer–polyarylate block copolymer as reactive compatibilizer for polyamide and acrylonitrile‐butadiene‐styrene blends

Styrene‐acrylonitrile random copolymer (SAN) and polyarylate (PAr) block copolymer were applied as a reactive compatibilizer for polyamide‐6 (PA‐6)/acrylonitrile‐butadiene‐styrene (ABS) copolymer blends. The SAN–PAr block copolymer was found to be effective for compatibilization of PA‐6/ABS blends. With the addition of 3.0–5.0 wt % SAN–PAr block copolymer, the ABS‐rich phase could be reduced to a smaller size than 1.0 μm in the 70/30 and 50/50 PA‐6/ABS blends, although it was several microns in the uncompatibilized blends. As a result, for the blends compatibilized with 3–5 wt % block copolymer the impact energy absorption reached the super toughness region in the 70/30 and 50/50 PA‐6/ABS compositions. The compatibilization mechanism of PA‐6/ABS by the SAN–PAr block copolymer was investigated by tetrahydrofuran extraction of the SAN–PAr block copolymer/PA‐6 blends and the model reactions between the block copolymer and low molecular weight compounds. The results of these experiments indicated that the SAN–PAr block copolymer reacted with the PA‐6 during the melt mixing process via an in situ transreaction between the ester units in the PAr chain and the terminal amine in the PA‐6. As a result, SAN–PAr/PA‐6 block copolymers were generated during the melt mixing process. The SAN–PAr block copolymer was supposed to compatibilize the PA‐6 and ABS blend by anchoring the PAr/PA‐6 and SAN chains to the PA‐6 and ABS phases, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2300–2313, 2002     

Control of interchange reactions of polycarbonate/polyarylate blends and their influence on physical behavior

Blends of polycarbonate of bisphenol A (PC) and a polyarylate of bisphenol A (PAr) are susceptible to showing interchange reactions in the melt state. The control of these reactions was carried out by means of the observation of the torque required to turn the Brabender and of its increase against the time due to copolymer formation in the processing equipment. Based on this variation and on glass transition temperature (T_g) measurements, the possibility of an exchange reaction in two steps in this blend was suggested. T_g measurements in melt- and solvent-cast blends also showed that this mixture is immiscible at all compositions and that, by copolymer evolution, a single T_g intermediate between those of the individual constituents can be found in all compositions. The influence of immiscibility on the mechanical properties of the blends was shown by the appearance of a minimum in large-strain properties at about 25% PAr. The behavior of the transesterified blends was very different showing a clear improvement of the tensile properties compared with those of the corresponding blends.     

PBT/PAr mixtures: Influence of interchange reaction on mechanical and thermal properties

The effect of the interchange reactions in PBT/PAr blends on thermal and mechanical properties has been studied as well as the influence of the concentration of tetrabutyltitanate on these properties. These studies have been carried out by means of differential scanning calorimetry (DSC) and tensile tests. The results based on DSC studies allow us to conclude that the capacity of the transesterified blends to crystallize decreases when compared with the physical blends, due to the formation of copolymers. Furthermore, an enhanced effect is observed when the amount of the catalyst is increased. In addition, a slight decrease in the low deformation mechanical properties and a significant increase in the deformation at break is observed as a consequence of the interchange reactions. The presence of tetrabutyltitanate, which accelerates the interchange reactions, has a 2-fold effect on these properties. On the one hand, it enhances the aforementioned process, but on the other hand, the associated effect of the degradation reactions decreases the mechanical properties, particularly those of the deformation at break. © 1996 John Wiley & Sons, Inc.     

Compatibilization of Polyamide‐6/Polyarylate Blends by Means of an Ionomer

Summary: Polyamide‐6 (PA6)/polyarylate of bisphenol A (PAr) blends rich in PA6 and modified with an additional 15% poly[ethylene‐co‐(methacrylic acid)] partially neutralized with zinc (PEMA‐Zn) as a compatibilizer were obtained by melt mixing. Their phase structure, morphology, and mechanical performance were compared with those of the corresponding binary blends. The ternary blends were composed of a PA6 amorphous matrix and a dispersed PAr‐rich phase in which reacted PA6 and PEMA‐Zn were present. Additionally, minor amounts of a crystalline PA6 phase, and a PEMA‐Zn phase were also present. The chemical reactions observed led to a clear decrease in the dispersed particle size when PEMA‐Zn was added, indicating compatibilization. Consequently, the mechanical behavior of the blends with PEMA‐Zn improved, leading, mainly in the case of the blend with 10% PAr, to significant increases in both ductility and impact strength with respect to those of the binary blends. These increases were more remarkable than the slight decrease in stiffness as a consequence of the rubbery nature of the compatibilizer.

Cryogenically fractured surface of the PA6/PAr‐PEMA‐Zn 70/30‐15 ternary blend.     

Studies on blends of binary crystalline polymers: Miscibility and crystallization behavior in PBT/PAr(I27-T73)

The miscibility and crystallization behavior of binary crystalline blends of poly(butylene terephthalate) [PBT] and polyarylate based on Bisphenol A and a 27/73 mole ratio of isophthalic and terephthalic acids [PAr(I27-T73)] have been investigated by differential scanning calorimetry (DSC). This blend system exhibits a single composition-dependent glass transition temperature over the entire composition range. The equilibrium melting point depression of PBT was observed, and Flory interaction parameter χ₁₂ = −0.96 was obtained. These indicate that the blends are thermodynamically miscible in the melt. The crystallization rate of PBT decreased as the amount of PAr(I27-T73) increased, and a contrary trend was found when PAr(I27-T73) crystallized with the increase of the amount of PBT. The addition of high-T_g PAr(I27-T73) would suppress the segmental mobility of PBT, while low-T_g PBT would have promotional effect on PAr(I27-T73). The crystallization rate and melting point of PBT were significantly influenced when the PAr(I27-T73) crystallites are previously formed. It is because not only does the amorphous phase composition shift to a richer PBT content after the crystallization of PAr(I27-T73), but also the PAr(I27-T73) crystal phase would constrain the crystallization of PBT. Thus, effects of the glass transition temperature, interaction between components, and previously formed crystallites of one component on the crystallization behavior of the other component were discussed and compared with blends of PBT and PAr(I-100) based on Bisphenol A and isophthalic acid.     

Polyarylate/polyamide 6 blends: A calorimetric study

Summary A calorimetric study has been done of the miscibility of blends composed of polyarylate (PAr) and poly(-caprolactam) (polyamide 6, nylon 6). The thermal transitions of blends subjected to two different thermal treatments have been determined. Two glass transitions have been observed in the blends irrespective of the thermal history. These glass transitions indicate the existence of two amorphous phases in the blends, a practically pure nylon phase and a mixed PAr/nylon 6 phase. The variation of the melting temperature of nylon with the blend composition is in good agreement with the existence of phase separation in the blends. However, the melting heat shows a slightly positive deviation from linearity when it is represented against the blend composition.     

Compatibilized poly(ether imide)/amorphous polyamide blends by means of poly(ethylene terephthalate) addition

Compatibilized poly(ether imide)/amorphous polyamide (PEI/a‐PA) blends were obtained in the melt state by substitution of 20% PEI by poly(ethylene terephthalate), PET. The two amorphous phases of the blends comprised both a miscibilized 80/20 PEI/PET blend and an a‐PA‐rich phase in which small amounts of PET and probably PEI were present. The presence of PET in the two phases of most of the blends was the main reason for the clear decrease in the particle size that indicated compatibilization. The smaller interfacial tension of the blends after PET addition also proved that compatibilization had occurred. The deviation of the modulus with respect to the direct rule of mixtures was positive in PEI‐rich blends and negative in the blends very rich in a‐PA. The modulus values were tentatively attributed to a different orientation of the components of the blends in the blends and in the neat state. The clear increases in ductility and the impact strength after PET addition further demonstrated the compatibilization effect of PET. POLYM. ENG. SCI., 46: 1292–1298, 2006. © 2006 Society of Plastics Engineers     

Binary blends containing a commercial polyarylate

A commercial polyarylate (PAr), a copolyester of Bisphenol-A with 50 percent terephthalate-50 percent isophthalate, has been characterized by means of a combination of gel permeation chromatography and viscometry. It has been studied as first component of a series of polymer blends. The presence of either one glass transition temperature (T_g) or two has been used as a criterion to determine the miscibility of each blend. In some cases, the possible incidence of transesterification reactions has been considered.     

Rheological properties of hyperbranched polymer/poly(ethylene terephthalate) reactive blends

The rheological properties in solution, in shear and in uniaxial elongation of poly(ethylene terephthalate) (PET) reacted together with hyperbranched polymers (HBPs) were investigated. Two different PET grades, of low and high molecular weights, were compounded with sub‐ to over‐stoichiometric concentrations of HBPs of second and fourth pseudo‐generation, and subsequently subjected to a solid‐state polycondensation (SSP). The formation of microgels, which occurs at high HBP concentration, gave rise to a large increase in melt elasticity and a related decrease in melt strength. At low HBP concentrations, the complex viscosity of the unreacted HBP/PET was considerably reduced, thus demonstrating a lubrication effect of the HBP molecules. During SSP, the intrinsic and shear viscosities exhibited a gradual increase, which was similar for both PET and HBP/PET blends, and was correlated to an increase in molecular weight, through linear‐chain extension and branching reactions. The elongational viscosity of the reactive blends was also increased as a function of reaction time, and this increase was much larger in the case of the HBP/PET blends. A 400% increase in melt strength of the PET was obtained by combining SSP and trace amounts of an HBP of second generation, without any decrease in drawability.     

Partially miscible blends based on a polyarylate and poly(trimethylene terephthalate)

The miscibility of blends of a polyarylate (PAr) with poly(trimethylene terephthalate) (PTT) was investigated in the whole composition range by DSC measurements. With the exception of the 90/10 composition, which was fully miscible, the blends showed partial miscibility, and contained a nearly pure PTT phase and a PAr‐rich phase with 18% PTT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1559–1561, 2004     

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.     

Transesterification reactions in triphenyl phosphite additivated‐poly(ethylene terephthalate)/poly(ethylene naphthalate) blends

The occurrence of transesterification reactions in poly(ethylene terephthalate) (PET)/poly(ethylene naphthalate) (PEN) blends prepared in presence of triphenyl phosphite (TPP) was investigated. When PEN was processed with TPP, which is a known chain extender for PET, chain extension reactions also took place. Torqueprocessing time curves obtained during preparation of 75/25 PET/PEN blends containing TPP, showed a build‐up profile followed by a fast decrease that was interpreted as chain extension between blend components and degradation due to phosphite residues formation, respectively. Although transesterification inhibition was expected, this type of reaction was not suppressed by TPP.     

Miscibility and interchange reactions in blends of bisphenol-A-type epoxy resin and poly(ethylene terephthalate)

Blends of diglycidyl ether of bisphenol A (DGEBA) and poly(ethylene terephthalate) (PET) were prepared by solution casting from 1,1,2,2-tetrachloroethane. The miscibility and interchange reactions in DGEBA–PET blends were studied by differential scanning calorimetry (DSC) and optical microscopy. PET was found to be miscible with DGEBA, as revealed by the existence of a single composition-dependence glass transition temperature (T_g). Interchange reactions between DGEBA and PET components in the blends at elevated temperatures were proven by appearance of the enhanced glass transition temperatures and the marked decrease in the crystallinity of PET. These results are attributed to the formation of copolymers based on the blend components due to interchange reactions. The morphological observations confirmed that there existed interchange reactions between DGEBA and PET. There also existed a self-crosslinking reaction among the DGEBA molecules. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 639–647, 1999     

Improvement of Mechanical Properties of Poly(butylene terephthalate)/Polyarylate Blends with Various Compositions via Zone Drawing-Zone Annealing

Abstract

Poly(butylene terephthalate)/polyarylate (PBT/PAr) blends of various compositions were subjected to a series of thermal and mechanical treatments. The evolution of the structure together with the static mechanical properties of produced fibers were investigated. It was found that zone drawing-zone annealing at 140 and 190[ddot] C markedly improves the blend mechanical properties: the Young modulus increases up to 5 times, the tensile strength-up to 10 times (compared to neat PBT) and up to 5 times (compared to neat PAr), the elongation at break drops 50–100 times with the rise of PAr content. The highest values of modulus and strength are obtained for blends containing between 10 and 35% (by wt) PAr. The observed improvement is explained by the substantial chain axis orientation and enhanced crystallization. of PBT offered by the zone drawing-zone annealing process, as proven by wide angle X-ray diffraction and birefrigent tests. Finally, a conclusion is drawn that after the appropriate treatments the PBT/PAr blends represent microfibrillar reinforced composites, similarly to other polymer blends for which the same improvements in the mechanical properties are known to be due to the microfibrillar reinforcing effect. The PBT microfibrils are visualized by observations using scanning electron microscope.     

Phase behavior of polyarylate blends

Melt mixtures of a polyarylate based on bisphenol A and tere/isophthalates were made with poly(ethylene terephthalate), several cyclohexane dimethanol-based polyesters, polycarbonate, and the poly(hydroxy ether) of bisphenol A. The phase behavior was determined using classical methods. With minimum time and temperature exposure, polyarylate exhibits phase separation with poly(ethylene terephthalate) (PET) at >30 wt % PET. With moderate time and temperature exposure, adequate ester exchange occurs with polyarylate/PET blends to yield single-phase behavior. The activation energy of the ester-exchange reaction was determined to be 37.0 kcal/mole. Under minimum time and temperature exposure conditions, miscibility of polyarylate with three different cyclohexane dimethanol-based polyesters was observed. A polyarylate-polycarbonate 50:50 mixture was shown to be phase separated under minimum mixing conditions but capable of exchange reactions to yield single-phase behavior with proper time and temperature exposure. Likewise, a 70:30 polyarylate-poly(hydroxy ether of bisphenol A) blend was phase separated as mixed, but with further elevated temperature exposure, a cross-linked single-phase system resulted. The density versus composition of the polyarylate-PET blends was linear with the phase-separated systems but exhibited a slight densification with the miscible systems produced by higher temperature exposure. The glass transition of the miscible polyarylate-polyester blends exhibited a significant deviation (lower) than predicted by a linear or Fox equation prediction. This was attributed to the low value of ΔC_p (specific heat difference between the glass and rubber states) of polyarylate as noted by the Couchman equation to be a major factor in the T_g versus composition relationship. The optical characteristics of the blends paralleled the observed phase behavior as single-phase blends were all transparent (in the amorphous state) whereas phase-separated blends were translucent to opaque. These results clearly demonstrate the importance of ester-exchange or transesterification reactions in the phase behavior of blends of polymers capable of these reactions.     

Phase morphologies and mechanical properties of high‐impact polystyrene (HIPS) and polycarbonate blends compatibilized with polystyrene and polyarylate block copolymer

Phasemorphology and mechanical properties of blends of high‐impact polystyrene (HIPS) and polycarbonate (PC) blends compatibilized with a polystyrene (PS) and polyarylate (PAr) (PS–PAr) block copolymer were investigated. Over a broad range of composition from 50/50 through 30/70, HIPS/PC blends formed cocontinuous structures induced by the flow during the extrusion or injection‐molding processes. These cocontinuous phases had heterogeneity between the parallel and perpendicular directions to the flow. The micromorphology in the parallel direction to the flow consisted of stringlike phases, which were highly elongated along the flow. Their longitudinal size was long enough to be longer than 180 μm, while their lateral size was shorter than 5 μm, whereas that in the perpendicular direction to the flow showed a cocontinuous phase with regular spacing due to interconnection or blanching among the stringlike phases. The PS–PAr block copolymer was found to successfully compatibilize the HIPS/PC blends. The lateral size of the stringlike phases could be controlled both by the amount of the PS–PAr block copolymer added and by the shear rate during the extrusion or injection‐molding process without changing their longitudinal size. The HIPS/PC blend compatibilized with 3 wt % of the PS–PAr block copolymer under an average shear rate of 675 s^?1 showed a stringlike phase whose lateral size was reduced almost equal to the rubber particle size in HIPS. The tensile modulus and yield stress of the HIPS/PC blends could be explained by the addition rule of each component, while the elongation at break was almost equal to that of PC. These mechanical properties of the HIPS/PC blends can be explained by a parallel connection model independent of the HIPS and PC phases. On the other hand, the toughness factor of the HIPS/PC blends strongly depended on the lateral size of the stringlike phases and the rubber particle size in the HIPS. It was found that the size of the string phases and the rubber particle should be smaller than 1.0 μm to attain a reasonable energy absorbency by blending HIPS and PC. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2347–2360, 2001