Compatibility of poly(ethylene 2,6-naphthalate) and poly(butylene 2,6-naphthalate) blends

Blends prepared from poly(ethylene 2,6-naphthalate) (PEN) and poly(butylene 2,6-naphthalate) (PBN) show only partial miscibility judged from their glass transition temperatures. Two distinct mechanical behaviors are observed: brittle for the blends < 20 wt% of PBN, while ductile > 20 wt% of PBN. The experimental modulus and strength values of the blends are within the predicted values according to Kleiner and Paul models, respectively. This means that PEN/PBN blends are somewhat compatible based on their tensile properties. Especially for 20 wt% of PBN blend, the high modulus and strength are observed. The viscosity of the blend is high, which may imply a somewhat entangled morphology in the amorphous state.     

Photodegradation of poly(ethylene 2,6-naphthalate) films

Poly(ethylene 2,6-Naphthalate) films were irradiated in air by various light sources. By means of a spectral irradiator and a UV carbon arc, the most effective wavelength was determined as about 382 mμ. For a wavelength shorter than 375 mμ, the insolubilization reaction occurs only at the surface layer, while at 382 mμ, the chain scission and insolubilization occur at the same time throughout the depth. Some observations on the change of the fluorescence spectra upon UV irradiation are described.     

Two-stage drawing of poly(ethylene 2,6-naphthalate)

Initially amorphous and semicrystalline films of poly(ethylene 2,6-naphthalate) with different molecular weights were drawn by two-stage drawing, that is, coextrusion at low temperatures (25–160°C) followed by tensile drawing at high temperatures (200–245°C). Both films could be drawn up to a draw ratio of 8–10 by this method under controlled conditions. The tensile modulus and strength of drawn samples were greatly affected by the draw temperature for the first stage, predrawn morphology, and molecular weight. The remarkable effects of these variables on the tensile properties are closely related to the difference in the resultant amorphous chain orientation of the samples, reflecting the disentanglements and chain slippage during drawing, and the dissipation of chain orientation after processing.     

Photochemical reactions in commercial poly(ethylene 2,6-naphthalate)

The photodegradation of poly(ethylene 2,6-naphthalate) is examined by absorption and emission spectroscopy and by flash photolysis techniques. A comparison of the emission spectra with that of a model compound 2,6-dimethynaphthalate (DMN) shows that the chromophoric species responsible for light absorption in the near ultraviolet is the unit structure of the polymer itself. A flash photolysis study of DMN indicates that the major primary process in photodeterioration of the polymer involves scission by decarboxylation at the naphthyl-carbon bond.     

Crystallization behavior and morphology of poly(ethylene 2,6-naphthalate)

The crystallization behavior and morphology of poly(ethylene 2,6-naphthalte) (PEN) were investigated by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM) and transmission electron microscopy (TEM). POM results revealed that PEN crystallized at 240 °C shows the coexistence of α and β-form spherulite morphology with different growth rates. In particular, when PEN crystallized at 250 °C, the morphology of spherulites showed a squeezed peanut shape. The Avrami exponents decreased from 3 to 2.8 above the crystallization temperature of 220 °C, indicating a decrease in growth dimension. Analysis from the secondary nucleation theory suggests that PEN crystallized at 240 °C has crystals with both regime I and regime II. In TEM observation, the ultra-thin PEN film crystallized at 200 °C showed the spherulitic texture with characteristic diffractions of α-form, while PEN crystallized at 240 °C generated an axialite structure with only β-form diffraction patterns. In addition, despite a long crystallization time of 24 h, amorphous regions were also observed in the same specimen. It was inferred that the initiation of PEN at 240 °C generates only β-form crystals from axialite structures.     

PEN/PET共混物结晶行为研究

用差示扫描量热法(DSC)研究了不同共混比例PEN/PET共混物的熔体结晶行为,并进行了等温结晶动力学测定。结果表明:随着两种组分向中间比例(50/50)靠近,共混物的熔融温度越低,结晶速率也越慢。     

The effect of transreactions on phase behavior in poly(ethylene 2,6-naphthalate) and poly(ethylene isophthalate) blends

The effect of transreactions on the phase behavior in poly(ethylene 2,6-naphthalate) and poly(ethylene isophthalate) blends was investigated by using differential scanning calorimetry. The transreactions between two polymers were confirmed by ¹H nuclear magnetic resonance. At the beginning step of transreactions, the blend samples show two glass transitions. However, after transreactions occur to some extent (i.e., when the degree of randomness is >0.4), a single glass transition is observed. As the transreactions proceed, the composition difference between ethylene 2,6-naphthalate-rich and ethylene isophthalate-rich phases lessens. Additionally, the weight fraction of each phase decreases because of the increment of interfacial fraction with the lapse of reaction time. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1851–1858, 1999     

Rapid crystallization of poly(ethylene 2,6-naphthalate) via aryl amide derivatives

ABSTRACT

A very small amount of aryl amide derivative (TMB-5) was used for nucleating Poly(ethylene 2,6-naphathalate) (PEN) by melt blending. The crystalline temperature, crystallinity, and nucleation efficiency of the composites were increased as a result of the addition of TMB-5. The half-time of crystallization decreased upon the addition of TMB-5 and the work required in folding polymer chains were reduced simultaneously in the polymer mixtures. The crystal size of the PEN/TMB-5 blends became smaller due to the increase of nucleation sites. The TMB-5 had no effect on the PEN crystal type. TMB-5 slightly increased the impact strength of PEN.     

Crystallization kinetics and nucleation activity of silica nanoparticle-filled poly(ethylene 2,6-naphthalate)

Silica nanoparticle-filled poly(ethylene 2,6-naphthalate) (PEN) composites were melt-blended to improve the mechanical and rheological properties of PEN. The melt viscosity and total torque values of the composites were reduced by the silica content. The crystallization exothermic peak shifted to a higher temperature, and the overall crystallization time was reduced by increasing the silica content. Non-isothermal crystallization kinetics was analyzed using the Ozawa and Avrami theories, and a combined method. The combined method was successful in describing the non-isothermal crystallization of these composites. The crystallization activation energy calculated using Kissinger's method was reduced, and the spherulite growth rate increased, with increasing silica content.A study of the nucleation activity, which indicated the influence of the filler on the polymer matrix, revealed that the fumed silica nanoparticles had a good nucleation effect on PEN.     

Uniaxial orientation and tensile properties of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blends

Amorphous films of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) (PET/PEN) blends with different blend ratios were uniaxially drawn by solid-state coextrusion and the structure development during solid state deformation was studied. As-prepared blends showed two T_gs. The lower T_g was ∼72 °C, independent of the blend ratio. In contrast, the higher T_g increased with increasing PEN content. Thus, the coextrusion was carried out around the higher T_g of the sample. At a given draw ratio of 5, which was close to the achievable maximum draw ratio, the tensile strength of the drawn samples from the initially amorphous state increased gradually with increasing PEN content. On the other hand, the tensile modulus was found to decrease initially, reaching a minimum at 40-60 wt% PEN, and then increased as the PEN content increased. The results indicate that we can get the drawn films with a moderate tensile modulus and a high tensile strength. The drawn samples from the blends containing 40-60 wt% of PEN showed a maximum elongation at break, and a maximum thermal shrinkage around 100 °C. Also, the degree of stress-induced crystallinity showed a broad minimum around the blend ratio of 50% of PEN. These morphological characteristics explained well the effects of blend ratio on the tensile modulus and strength of drawn PET/PEN blend films.     

Morphology and barrier properties of oriented blends of poly(ethylene terephthalate) and poly(ethylene 2,6-naphthalate) with poly(ethylene-co-vinyl alcohol)

Morphology and oxygen permeability studies were carried out for blends of poly(ethylene terephthalate), PET, and poly(ethylene 2,6-naphthalate), PEN, with poly(ethylene-co-vinyl alcohol), EVOH. PET/EVOH blends are seen as a possible substitute for poly(vinylidene chloride)-coated PET packaging films. The effects of several processing parameters such as draw temperature and draw ratio on blend morphology and barrier properties suggest that the morphology of the EVOH phase dictates to a large extent the oxygen permeabilities of these blends. The relationships between morphology and oxygen permeability and explained are explained by consideration of two-phase conduction models. The model of Fricke is found to be a good predictor of the barrier properties of the PET/EVOH system. The oxygen permeability of PET was reduced by a factor of 4.2 with the addition of 20 wt% EVOH and that of PEN by a factor of 2.7 with the addition of 15 wt% EVOH. Water vapor permeabilities and mechanical properties of PET and PEN were only slightly affected by the addition of 15 wt% EVOH.     

Thermal analysis and Raman spectroscopic studies of crystallization in poly(ethylene 2,6-naphthalate)

The combination of Fourier transform Raman spectroscopy and thermal analysis has been proved to be adequate for the study of the quantitative structural changes which take place in amorphous poly(ethylene 2,6-naphthalate) on annealing. Different conformer contents were found in the annealed samples depending on annealing conditions. In general, annealing of the amorphous poly(ethylene 2,6-naphthalate) from the glassy state induces a conformational transition of gauche to trans. The structure obtained during crystallization is characterized by a three-phase conformational model, including an amorphous phase, a rigid amorphous phase and a crystalline phase. The crystallization is further characterized by a three-zone process, firstly a primary crystallization process, secondly a variation of the rigid amorphous phase with a constant value of the crystalline phase and thirdly a secondary crystallization process. The bandwidth at half intensity at 1721 cm⁻¹ in the Raman spectrum varied between 32 cm⁻¹ for the complete amorphous phase and 7 cm⁻¹ for the total rigid phase, the sum of the rigid amorphous and crystalline phase. The bandwidth at half intensity at 1721 cm⁻¹ was directly related to the amount of the total rigid phase and confirmed by the variation of the heat capacity increase at the glass transition temperature. Two complementary bands in the Raman spectrum, at 1107 and 1098 cm⁻¹, were found to be related to the trans and gauche isomers. A difference was measured between the total trans content and the amount of rigid phase due to the presence of some trans conformations in the amorphous phase. The extrapolation of the bandwidth at half intensity at 1721 cm⁻¹ to the value of zero, corresponding to the complete crystalline phase, gave a melting enthalpy of 196 J/g and the corresponding density of the crystalline phase was 1.4390 g/cm³. A complete rigid phase structure was obtained by a melting enthalpy of 144 J/g and a density of 1.4070 g/cm³.     

Rheology and thermal properties of liquid crystalline copolyester and poly(ethylene 2,6-naphthalate) blends

Blends of a poly(ethylene 2,6-naphthalate) (PEN) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate) were prepared in a twin-screw extruder. Specimens for thermal properties were investigated by means of an instron capillary rheometer (ICR) and scanning electron microscopy (SEM). The blend viscosity showed a minimum at 10 wt% of LCP and increased with increasing LCP content above 10 wt% of LCP. Above 50% of LCP and at higher shear rate, phase inversion occured and the blend morphology was fibrous and similar to pure LCP. The ultimate fibrillar structure of LCP phase appeared to be closely related to the extrusion temperature. By employing a suitable deformation history, the LCP phase may be elongated and oriented such that a microfibrillar morphology can be retained in the solid state. Thermal properties of the LCP/PEN blends were studied using DSC and a Rheovibron viscoelastomer. These blends were shown to be incompatible in the entire range of the LCP content. For the blends, the T_g and Tm were unchanged. The half time of crystallization for the LCP/PEN blends decreased with increasing LCP content. Therefore, the LCP acted as a nucleating agent for the crystallization of PEN. The dimensional and thermal stability of the blends were increased with increasing LCP content. In studies of dynamic mechanical properties, the storage modulus (E′) was improved with increasing LCP content and synergistic effects were observed at 70 wt% of LCP content. The storage modulus for the LCP/PEN 70/30 blend is twice that of PEN matrix and exceeded pure LCP.     

Morphology and mechanical properties of liquid crystalline copolyester and poly(ethylene 2,6-naphthalate) blends

Blends of poly(ethylene 2,6-naphthalate) (PEN) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate), were prepared in a twin-screw extruder. Specimens for mechanical testing were prepared by injection molding. The morphology and mechanical properties were investigated by scanning electron microscopy (SEM) and an Instron tensile tester. SEM studies revealed that finely dispersed spherical domains of the liquid crystalline polymer (LCP) were formed in the PEN matrix, and the inclusions were deformed into fibrils from the spherical droplets with increasing LCP content. The morphology of the blends was found to be affected by their composition and a distinct skin-core morphology was found to develop in the injection molded samples of these blends. Mechanical properties were improved with increasing LCP content, and synergistic effects have been observed at 70 wt% LCP content whereas the elongation at break was found to be reduced drastically above 10 wt% of LCP content. This is a characteristic typical of chopped-fiber-filled composites. The improvement in mechanical properties is likely due to the reinforcement of the PEN matrix by the fibrous LCP phase as observed by scanning electron microscopy. The tensile and modulus mechanical behavior of the LCP/PEN blends was very similar to those of the polymeric composite, and the tensile strength and flexural modulus of the LCP/PEN 70/30 blend were two times the value of PEN homopolymer and exceeded those of pure LCP, suggesting LCP acts as a reinforcing agent in the blends.     

Crystal structure of poly(pentamethylene 2,6-naphthalate)

The crystal structure of poly(pentamethylene 2,6-naphthalate) (PPN) was determined by using X-ray diffraction and molecular modeling. The unit cell of PPN was found to be triclinic ( space group) with dimensions of a=0.457 nm, b=0.635 nm, c=2.916 nm, =121.6°, β=90.4°, γ=87.6°, and the calculated crystal density was 1.311 g cm⁻³. The unit cell contains one polymer chain with two repeating units. In the unit cell, the PPN backbone takes gauche/gauche conformation in the middle part of each pentamethylene unit, and two naphthalene rings are in face-to-face arrangement.     

Enthalpy relaxation in poly(ethylene terephthalate) and related polyesters

Enthalpic relaxation data are presented on poly(ethylene terephthalate), poly(ethylene naphthalate) and their copolymers. Analysis of these data allows the determination of the amount of energy absorbed at the glass transition, Q_t, and the location of the enthalpic recovery peak, T_max, as a function of the time of ageing of the samples. Ageing measurements were carried out for periods of up to 2016 h and at temperatures between 40 °C and 110 °C, depending upon the chemical composition of the system being investigated. The enthalpic relaxation rates are influenced by the chemical structure and reflect the effects of local order pinning the chains and influencing the rate of enthalpic recovery. © 2000 Society of Chemical Industry     

Unique nucleation of multi-walled carbon nanotube and poly(ethylene 2,6-naphthalate) nanocomposites during non-isothermal crystallization

Multi-walled carbon nanotube (MWCNT) and poly(ethylene 2,6-naphthalate) (PEN) nanocomposites are prepared by a melt blending process. There are significant dependence of non-isothermal crystallization behavior and kinetics of PEN/MWCNT nanocomposites on the MWCNT content and cooling rate. The incorporation of MWCNT accelerates the mechanism of nucleation and crystal growth of PEN, and this effect is more pronounced at lower MWCNT content. Combined Avrami and Ozawa analysis is found to be effective in describing the non-isothermal crystallization of the PEN/MWCNT nanocomposites. The MWCNT in the PEN/MWCNT nanocomposites exhibits much higher nucleation activity than any nano-scaled reinforcement. When a vary small quantity of MWCNT was added, the activation energy for crystallization is lower, then gradually increased, and becomes higher than that of pure PEN above 1.0 wt% MWCNT content. The incorporation of MWCNT improves the storage modulus and loss modulus of PEN/MWCNT nanocomposites.     

Light scattering studies on the crystalline morphology of stretched poly(ethylene 2,6-naphthalate) film

The crystalline morphology of poly(ethylene 2,6-naphthalate) (PEN) film obtained by uniaxial stretching at 145 °C (T_g + 25 °C) was investigated by use of a light scattering photometer equipped with a CCD camera system. The Hv scattering showed a symmetric, circular pattern at a low stretch ratio of λ < 3. The intensity profile became sharper with an increase in λ, suggesting that anisotropic crystal rods are randomly assembled and that the length of the rods increases with λ. At a high stretch ratio of λ ≥ 3, a double-cross-type pattern consisting of a broad rod-like pattern and sharp cross streaks was observed. The rod-like pattern became smaller and the streaks became sharper with an increase in λ. By the model calculation of the scattering pattern, the double-cross-type pattern is explained by the stacking of anisotropic crystal rods oriented in the stretch direction. As λ increases, the thickness of the rods and the number per stack increase, and the stacks and rods are slightly oriented in the stretch direction. The change in the wide angle X-ray diffraction pattern suggested that the ordering of the molecular chain in the crystal rods increases with increasing λ.     

Mesomorphic phase in oriented poly(pentamethylene 2,6-naphthalate)

The mesomorphic structure of poly(pentamethylene 2,6-naphthalate) (PPN) was investigated using a synchrotron X-ray scattering. The PPN fibers cold-drawn from the super-cooled amorphous state showed a smectic mesomorphic structure and further a crystalline phase at high strain. Based on the experimental evidence showing the split of amorphous halo up and down the equator and the conformational constraint suggested by the crystal structure refinement and computation, we suggested the smectic phase as S_CA where the mesogens are tilted against the layer surface normal and the tile direction is opposite between the neighboring layers.