Miscibility study on blend of thermotropic liquid crystalline polymers and polyester

The miscibility of thermotropic liquid crystalline polymers (TLCPs) and polyester blends was investigated with thermal and morphological analyses, as well as transesterification. TLCPs composed of 80 mol % para‐hydroxybenzoate (PHB) and 20 mol % poly(ethylene terephthalate) (PET) or 60 mol % PHB and 40 mol % PET, and polyesters such as PET and poly(ethylene 2,6‐naphthalate) (PEN) were melt blended in an internal mixer. DSC analyses were performed to investigate the thermal transition behavior and to obtain thermodynamic parameters. All the blends showed only a single glass‐transition temperature, which means they are partially miscible in the molten state. The Flory–Huggins interaction parameter was calculated employing the Nishi–Wang approach, and negative values were obtained except for the P(HB8‐ET2)/PEN blends. Transesterification was investigated using ¹H‐NMR, and the change of chemical shift compared to pure PET or P(HB‐ET)s was observed in the P(HB‐ET)/PET blends. An intermediate chemical shift value (4.83 ppm) was observed in the P(HB6‐ET4)/PEN blends, which indicates transesterification occurred. The fractured surface morphology of scanning electron micrographs showed that the interfaces between the LC droplets and matrix were not distinct. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1842–1851, 2003     

Preparation and characterization of poly(methyl methacrylate) beads

The phase behavior of Poly(ethylene terephthalate)/Poly(ethylene‐2,6‐naphthalate)/Poly(ethylene terephthalate‐co‐ethylene‐2,6‐naphthalate) (PET/PEN/P(ET‐co‐EN)) ternary blends in molten state was evaluated from differential scanning calorimetry (DSC) and NMR results as well as optical microscopic observations. Copolymer of ethylene terephthalate and ethylene‐2,6‐naphthalate was prepared by a condensation polymerization, which was a random copolymer with an intrinsic viscosity (IV) of 0.3 dL/g. The phase diagram of the ternary blends revealed that the miscibility of ternary blends in molten state was dependent on the fraction of P(ET‐co‐EN) in the blends and holding time of the blends at high temperatures above 280°C. With increase in the holding time, the fraction of copolymer in the blends necessary to induce the immiscible to miscible transition decreased. For the blends with longer holding time at 280°C, the phase diagram in molten state was irreversible against the temperature, although a reversibility was found for the blends with short holding time of 1 min at 280°C. The irreversibility of phase behavior was not explained simply by the increase of copolymer content produced during heat treatment. Complex irreversible physical and chemical interactions between components and change of phase structure of the blend in the molten state might influence on the irreversibility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Study on phase separation of PET/PEN blends by dynamic rheology

Blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) were processed into biaxially drawn films, and samples taken from the bi‐oriented films were then investigated by dynamic rheology experiments in the melt state. Storage modulus G′ and loss modulus G″ were determined in the frequency range of 10^?2–10² rad/s at temperatures between 260 and 300°C. Although the time–temperature superposition (TTS) principle was found to hold in the high frequency regime, a breakdown of TTS was observed at low frequencies, and the terminal behavior of the storage modulus G′ of the blends departs drastically from the terminal behavior observed for the blend components. This is caused by interfacial surface tension effects. The results indicate that despite the effect of transesterification reactions, the PET/PEN blend systems investigated consist of a microseparate phase of PEN platelets in a matrix of PET. This morphology is produced when the blends are processed into biaxially oriented PET/PEN films, and droplets of PEN are deformed into a lamellar structure consisting of parallel and extended, separate layers. The large interfacial surface area of the bi‐oriented PET/PEN blends leads to remarkably strong interfacial tension effects in dynamic rheology measurements. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization Study of Glassy PET/PEN Blends by Means of Real Time X-ray Scattering

Abstract

The crystallization of several blends of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6 naphthalene dicarboxylate) (PEN) has been investigated by wide angle- (WAXS) and small angle X-ray scattering (SAXS) using synchrotron radiation. The role of transesterification reactions, giving rise to a fully amorphous non-crystal-lizable material (copolyester) is brought up. For the blends rich in PET, crystallization temperatures (T_c ) of 105 and 117°C were used. For blends rich in PEN, crystaffization was performed at T_c =150 and 165°C, respectively. The time variation of the degree of crystallinity was fitted into an Avrami equation considering the induction time prior to the beginning of crystallization. The Avrami parameters, the half times of crystallization, as well as the nanostructure development (SAXS invariant and long period) for the blends, are discussed in relation to blend composition and are compared to the parameters observed for the homopolymers PET and PEN.     

Effects of electron beam irradiation on poly(ethylene 2,6‐naphthalate)/poly(ethylene terephthalate) blends

The effect of electron beam (EB) irradiation on the properties and compatibility of poly(ethylene 2,6‐naphthalate) (PEN)/poly(ethylene terephthalate) (PET) blends was investigated. Upon EB irradiation, PEN/PET blends underwent transesterification reactions, resulting in the formation of more random copolymers from the original binary pair. The degree of transesterification increased with dose rate, and all of the irradiated blends exhibited a single glass transition temperature. This indicated that transesterification reactions promoted by EB irradiation led to the formation of a single phase. Transesterification reactions promoted by EB irradiation led to more random copolymers, and the reduced regularity in the irradiated blends decreased the melting temperature. A higher degree of randomness and lower number‐average sequence lengths for the blend systems indicated that a more random chain structure was formed in the blends. The rheological measurements demonstrated that the irradiated PEN/PET blends were miscible. EB irradiation could promote transesterification reaction, thus enhancing the compatibility of PEN/PET blends.     

Glass‐transition and melting behavior of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

The glass‐transition temperatures and melting behaviors of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends were studied. Two blend systems were used for this work, with PET and PEN of different grades. It was found that T_g increases almost linearly with blend composition. Both the Gibbs–DiMarzio equation and the Fox equation fit experimental data very well, indicating copolymer‐like behavior of the blend systems. Multiple melting peaks were observed for all blend samples as well as for PET and PEN. The equilibrium melting point was obtained using the Hoffman–Weeks method. The melting points of PET and PEN were depressed as a result of the formation of miscible blends and copolymers. The Flory–Huggins theory was used to study the melting‐point depression for the blend system, and the Nishi–Wang equation was used to calculate the interaction parameter (χ₁₂). The calculated χ₁₂ is a small negative number, indicating the formation of thermodynamically stable, miscible blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 11–22, 2001     

Polymer blends of poly(ethylene‐2,6‐naphthalate) with polystyrene compatibilized by styrene‐glycidyl methacrylate copolymers. I. Rheology,morphology, and mechanical properties

The compatibilization of blends of poly(ethylene‐2,6‐naphthalate) (PEN) with polystyrene (PS), through the styrene‐glycidyl methacrylate copolymers (SG) containing various glycidyl methacrylate (GMA) contents, was investigated in this study. SG copolymers are able to react with PEN terminal groups during melt blending, resulting in the formation of desirable SG‐g‐PEN copolymers in the blend. These in situ formed copolymers tend to reside along the interface preferentially as the result of interfacial reaction and thus function as effective compatibilizers in PEN/PS blends. The compatibilized blends exhibit higher viscosity, finer phase domain, and improved mechanical properties. It is found that the degree of grafting of the in situ formed SG‐g‐PEN copolymer has to be considered as well. In blends compatibilized with the SG copolymer containing higher GMA content, heavily grafted copolymers would be produced. The length of the styrene segment in these heavily grafted copolymers would be too short to penetrate deep enough into the PS phase to form effective entanglements, resulting in the lower compatibilization efficiency in PEN/PS blends. Consequently, the in situ formation of SG‐g‐PEN copolymers with an optimal degree of grafting is the key to achieving the best performance for the eventually produced PEN/PS blends through SG copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 967–975, 2003     

On the interrelationship of transreaction with viscoelastic properties of poly(ethylene terephthalate)/poly(ethylene naphthalate) blends in the presence of nanoclay

An attempt was made to explore the effects of the interchange reactions on the viscoelastic behavior of binary blends based on poly(ethylene terephthalate) (PET)/poly(ethylene naphthalate) (PEN) and their nanocomposites. It was seen that with an increase in the number of extrusion runs and mixing temperature, the extent of reaction (X) and degree of randomness (RD) both increased, whereas the average sequence block lengths values were decreased. On the contrary, the blend composition did not play a significant role on X and RD values. Addition of nanoclay inhibited the transreactions in PET/PEN blends. The absence of crystallization peaks implied that the crystalline structure was destroyed as a result of blending and an amorphous system was created possibly due to the transreactions simultaneously with the formation of random copolymers inhibiting the crystallization process. The rheological investigations showed that the addition of PEN into the PEN/PET blends enhanced the storage modulus, loss modulus, and complex viscosity. The viscosity upswing observed at low‐frequency region in the case of nanocomposite systems evidently confirmed the occurrence of transreactions. Nonetheless, a significant increment in the viscoelastic properties was perceived in the presence of nanoclay corroborating the proper nanoclay distribution throughout the PET/PEN blend system. POLYM. ENG. SCI., 53:2556–2567, 2013. © 2013 Society of Plastics Engineers     

Role of 2‐hydroxyethyl end group on the thermal degradation of poly(ethylene terephthalate) and reactive melt mixing of poly(ethylene terephthalate)/poly(ethylene naphthalate) blends

In an attempt to minimize the acetaldehyde formation at the processing temperatures (280–300°C) and the outer–inner transesterification reactions in the poly (ethylene terephthalate) (PET)–poly(ethylene naphthalate) (PEN) melt‐mixed blends, the hydroxyl chain ends of PET were capped using benzoyl chloride. The thermal characterization of the melt‐mixed PET–PEN blends at 300°C, as well as that of the corresponding homopolymers, was performed. Degradations were carried out under dynamic heating and isothermal conditions in both flowing nitrogen and static air atmosphere. The initial decomposition temperatures (T_i) were determined to draw useful information about the overall thermal stability of the studied compounds. Also, the glass transition temperature (T_g) was determined by finding data, indicating that the end‐capped copolymers showed a higher degradation stability compared to the unmodified PET and, when blended with PEN, seemed to be efficient in slowing the kinetic of transesterification leading to, for a finite time, the formation of block copolymers, as determined by ¹H‐NMR analysis. This is strong and direct evidence that the end‐capping of the ? OH chain ends influences the mechanism and the kinetic of transesterification. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Crystallization kinetics of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

The crystallization kinetics of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends were investigated by DSC as functions of crystallization temperature, blend composition, and PET and PEN source. Isothermal crystallization kinetics were evaluated in terms of the Avrami equation. The Avrami exponent (n) is different for PET, PEN, and the blends, indicating different crystallization mechanisms occurring in blends than those in pure PET and PEN. Activation energies of crystallization were calculated from the rate constants, using an Arrhenius‐type expression. Regime theory was used to elucidate the crystallization course of PET/PEN blends as well as that of unblended PET and PEN. The transition from regime II to regime III was clearly observed for each blend sample as the crystallization temperature was decreased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 23–37, 2001     

Oxygen and carbon dioxide transport through high barrier polyester blends

The transport of oxygen and carbon dioxide through a set of random copolymer films based on poly(ethylene terephthalate) (PET) and poly(ethylene 2,6‐naphthalate) (PEN) were explored. Diffusivity and permeability of both gases decreased with increasing PEN content. The oxygen and carbon dioxide diffusion coefficients decreased 74 and 82% from pure PET to pure PEN, respectively. The presence of stiffer PEN moieties had an effect on the glass transition temperature (T_g) of PET/PEN blends and gas barrier. In the complete range of tested blends, the differential scanner calorimeter analysis displayed a single value of thermal glass transition temperature. As the PEN content was increased, the fractional free volume (FFV) and the diffusion coefficients of the blends were decreased. The Doolittle equation provided the best fit for diffusivity and FFV and showed that the gas transport behavior was better understood when it was taken into consideration the cohesive energy of blends. As the PEN content in films was increased, their rigidity and the glass/rubber transition temperature were increased, and their capacity to be penetrated by small molecules like O₂ and CO₂ was decreased. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Charge storage of ternary polymer blends based on poly(phenylene ether)

BACKGROUND: Charge storage capability is a fundamental property of polymers used in electromechanical transducer applications. In this work, the charge retention of ternary blends of poly(phenylene ether) and polystyrene modified with poly(styrene‐co‐acrylonitrile), polystyrene‐block‐poly(ethylene‐co‐butylene)‐block‐polystyrene or polystyrene‐block‐polyisobutylene‐block‐polystyrene (SIBS) triblock copolymers was correlated with the blend composition, final morphology and the chemical structure of the components. RESULTS: It was determined that the charge storage capability is favoured by a finely dispersed and non‐interconnected phase and can be reduced by high polarity or low molecular weight of the blend components. Additionally, the molecular weight and the amount of styrene of the copolymers also determined the phase morphology, which in turn affected the charge retention. The use of SIBS for the ternary blends, especially in small quantities, significantly improved the charge storage. As such, 100 µm films with a surface potential of about 400 V were able to retain up to 240 V (60%) after 24 h at 130 °C. CONCLUSION: The electret behaviour of the polymer blends was influenced by a complex relationship between chemical structure, molecular weight and phase morphology. Copyright © 2009 Society of Chemical Industry     

Investigation of thermal behavior and decomposition kinetic of PET/PEN blends and their clay containing nanocomposites

Blends of Poly(ethylene terephthalate), (PET), and poly(ethylene naphthalene 2,6-dicarboxylate), (PEN), were prepared in a twin-screw extruder. Samples were investigated by differential scanning calorimetry (DSC) and proton nuclear magnetic resonance (¹H NMR) measurements to evaluate the extent of transesterification reaction. X-ray diffraction (XRD) test was performed to examine the effect of transesterification reactions on crystalline structure of the blends. Thermogravimetry analysis (TGA) was used to study thermal decomposition of the blends which could be explained by the level of transesterification reaction for various blend compositions. The kinetic of the decomposition reaction was analyzed by Freeman-Carroll and Chang models. It was found that these two methods were acceptable models for describing the thermal decomposition of the blends however, the Chang model showed better correlation with the experimental data as compared to the other model. Results revealed that progress of transesterification reaction in blends depends on temperature and mixing time, which have dominant role in thermal behavior and decomposition kinetic of the blends. Effect of nanoclay on transesterification reactions and degradation behavior was also investigated. It was found that the nanoclay inhibited the transesterification reactions and reduced the thermal stability of the blends. PET degraded much faster than PEN in O₂ environment while, an opposite trend was observed in N₂ atmosphere.     

Antistatic performance and morphological observation of ternary blends of poly(ethylene terephthalate), poly(ether esteramide), and ionomers

Blends of poly(ethylene terephthalate) (PET) and poly (ether esteramide) (PEEA), which is known as an ion conductive polymer, were prepared by melt mixing using a twin screw extruder. Antistatic performance of the molded plaques and the effects of adding ionomers such as lithium neutralized poly(ethylene‐co‐methacrylic acid) copolymer(E/MAA‐Li), magnesium neutralized poly(ethylene‐co‐methacrylic acid) copolymer(E/MAA‐Mg), and zinc neutralized poly(ethylene‐co‐methacrylic acid) copolymer (E/MAA‐Zn) were investigated. Antistatic effect of adding poly(ethylene‐co‐methacrylic acid) copolymer(E/MAA) and polystyrene, and poly(ethylene naphthalate) (PEN) into PET/PEEA blends were also investigated. Here we confirmed that lithium ionomer worked the most effectively in those blend systems. We also confirmed that E/MAA worked to enhance the antistatic performance of PET/PEEA blends. Morphological study of these ternary blends system was conducted by TEM. Specific interaction between PEEA and E/MAA‐Li, and E/MAA were observed. Those ionomers and copolymer domains were encapsulated by PEEA, which could increase the surface area of PEEA in PET matrix. This encapsulation effect explains the unexpected synergy for the static dissipation performance on addition of ionomers and E/MAA to PET/PEEA blends. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

In situ AFM study of near‐surface crystallization in PET and PEN

The surface crystallization behavior of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6‐naphthalate) (PEN) spin‐coated thin films was compared by means of atomic force microscopy (AFM) with an in situ heating stage. As the films were heated up stepwise, characteristic surface crystals appeared at a crystallization temperature (T_c) in the near‐surface region which is about 15 °C under the bulk T_c, and were replaced by bulk crystals when the temperature was increased to the bulk T_c. In the case of films whose thickness is less than 70 nm (PET) and 60 nm (PEN), significant increases in the bulk T_c were observed. Scanning force microscopy (SFM) force‐distance curve measurements showed that the glass transition temperature (T_g) of the near‐surface region of PET and PEN were 22.0 and 26.6 °C below their bulk T_g (obtained by DSC). After the onset of surface crystallization, edge‐on and flat‐on crystals appeared at the free surface of PET and PEN thin films, whose morphologies are very different to those of the bulk crystals. Although the same general behavior was observed for both polyesters, there are significant differences both the influence of the surface and substrate on the transition temperatures, and in morphology of the surface crystals. These phenomena are discussed in terms of the differences in the mobility of polymer chains near the surface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44269.     

Effects of tetramethylpolycarbonate‐block‐poly(styrene‐co‐acrylonitrile) copolymers containing various amounts of acrylonitrile on the interfacial properties of polycarbonate and poly(styrene‐co‐acrylonitrile) blends

Tetramethylpolycarbonate‐block‐poly(styrene‐co‐acrylonitrile) (TMPC‐block‐SAN) block copolymers containing various amounts of acrylonitrile (AN) were examined as compatibilizers for blends of polycarbonate (PC) with poly(styrene‐co‐acrylonitrile) (SAN) copolymers. To explore the effects of block copolymers on the compatibility of PC/SAN blends, the average diameter of the dispersed particles in the blend was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fibre retraction technique and an asymmetric double‐cantilever beam fracture test. Reduction in the average diameter of dispersed particles and effective improvement in the interfacial properties was observed by adding TMPC‐block‐SAN copolymers as compatibilizer of PC/SAN blend. TMPC‐block‐SAN copolymer was effective as a compatibilizer when the difference in the AN content of SAN copolymer and that of SAN block in TMPC‐block‐SAN copolymer was less than about 10 wt%. Copyright © 2004 Society of Chemical Industry     

Effects of molecular weight on phase structure of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

The phase structure of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends was studied in relation to the molecular weight. The samples were prepared by both solution blends, which showed two glass‐transition temperatures (T_g), and melt blends (MQ), which showed a single T_g, depending on the composition of the blends. The T_g of the MQ series was independent of the molecular weight of the homopolymer, although the degree of transesterification in the blends was affected by the molecular weight. The MQ series showed two exotherms during the heating process of a differential scanning calorimetry scan. The peak temperature and the heat flow of the exotherms were affected by the molecular weight of the homopolymers. The strain‐induced crystallization of the MQ series suggested the independent crystallization of PET and PEN. Based on the results, a microdomain structure of each homopolymer was suggested. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2428–2438, 2005     

Miscibility and transesterification in ternary blends of poly(ethylene naphthalate)/poly(pentamethylene terephthalate)/poly(ether imide)

Miscibility and morphology of poly(ethylene 2,6‐naphthalate)/poly(pentamethylene terephthalate)/poly(ether imide) (PEN/PPT/PEI) blends were studied by differential scanning calorimetry (DSC), optical microscopy (OM), proton nuclear magnetic resonance imaging (¹H‐NMR), and wide‐angle X‐ray diffraction (WAXD). OM and DSC results from ternary blends revealed the immiscibility of PEN/PPT/PEI blends, but ternary blends of all compositions were phase‐homogeneous following heat treatment at 300°C for over 60 min. Annealing samples at 300°C yielded an amorphous blend with a clear and single T_g at the final state. Experimental data from ¹H‐NMR revealed that PEN/PPT copolymers (ENPT) were formed by the so‐called transesterification. The effect of transesterification on glass transition and crystallization was discussed in detail. The sequence structures of the copolyester were identified by triad analysis, which showed that the mean sequence lengths became shorter and the randomness increased with heating time. The results reveal that a random copolymer improved the miscibility of the ternary blends, in which, the length of the homo segments in the polymer chain decreased and the crystal formation was disturbed because of the irregularity of the structure, as the exchange reaction proceeded. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3840–3849, 2006     

Microstructure and crystallization of melt‐mixed poly(ethylene terephthalate)/poly(ethylene isophthalate) blends

Physical blends of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI), abbreviated PET/PEI (80/20) blends, and of PET and a random poly(ethylene terephthalate‐co‐isophthalate) copolymer containing 40% ethylene isophthalate (PET₆₀I₄₀), abbreviated PET/PET₆₀I₄₀ (50/50) blends, were melt‐mixed at 270°C for different reactive blending times to give a series of copolymers containing 20 mol % of ethylene isophthalic units with different degrees of randomness. ¹³C‐NMR spectroscopy precisely determined the microstructure of the blends. The thermal and mechanical properties of the blends were evaluated by DSC and tensile assays, and the obtained results were compared with those obtained for PET and a statistically random PETI copolymer with the same composition. The microstructure of the blends gradually changed from a physical blend into a block copolymer, and finally into a random copolymer with the advance of transreaction time. The melting temperature and enthalpy of the blends decreased with the progress of melt‐mixing. Isothermal crystallization studies carried out on molten samples revealed the same trend for the crystallization rate. The effect of reaction time on crystallizability was more pronounced in the case of the PET/PET₆₀I₄₀ (50/50) blends. The Young's modulus of the melt‐mixed blends was comparable to that of PET, whereas the maximum tensile stress decreased with respect to that of PET. All blend samples showed a noticeable brittleness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3076–3086, 2003     

Morphological study by TEM on uniaxially oriented thin films of PET, PEN and their blends

Uniaxially oriented thin films of poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalene dicarboxylate) (PEN) and their blends were prepared by applying shear strain to their respective melts, and the resulting morphologies were studied by transmission electron microscopy. Selected-area electron diffraction of each film revealed well-defined uniaxial orientation of polymer chains in the shearing direction. In the uniaxially oriented thin film of PEN, stacked-lamellar structure with the average long period of 27 nm consisting of a crystalline region about 15 nm thick and an amorphous one about 12 nm thick was found here and there in the dark-field image: PEN-type. On the other hand, stacked-lamellar structure was rarely observed in the case of PET: PET-type. In PET/PEN blends, the morphologies changed from the PET-type to the PEN-type with increasing content of PEN.