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。     

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     

Properties of poly(ethylene terephthalate)/poly(ethylene naphthalate) blends

Blends composed of poly(ethylene terephthalate) (PET) as the majority component and poly(ethylene naphthalate)(PEN) as the minority component were melt-mixed in a single screw extruder at various PET/PEN compound ratios. Tensile and flexural test results reveal a good PET/PEN composition dependence, indicating that the compatibility of the blends is effective in a macrodomain. In thermal tests, single transitions for T_g, T_m and T_c (crystallization temperature), respectively, are observed from DSC as well as single T_g from DMA except for 50/50 blends. These results suggests that the compatibility is sufficient down to the submicron level. Moreover, isothermal DSC tests along with Avrami analysis indicate that PET's crystallization is significantly retarded when blended with PEN. Results in this study demonstrate that PEN is a highly promising additive to improve PET's spinnability at high speeds.     

Primary structure and physical properties of poly(ethylene terephthalate)/poly(ethylene naphthalate) resin blends

The morphology and properties of blends of poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) that were injection molded under various conditions were studied. Under injection molding conditions that make it possible to secure transparency, blends did not show clear crystallinity at blending ratios of more than 20 mol% in spite of the fact that crystallinity can be observed in the range of PEN content up to 30 mol%. Because both transparency and crystallinity could be secured with a PEN 12 mol% blend, this material was used in injection molding experiments with various injection molding cycles. Whitening occurred with a cycle of 20 sec, and transparency was obtained at 30 sec or more. This was attributed to the fact that transesterification between PET and PEN exceeded 5 mol% and phase solubility (compatibility) between the PET and PEN increased when the injection molding time was 30 sec or longer. However, when the transesterification content exceeded 8 mol%, molecularly oriented crystallization did not occur, even under stretching, and consequently, it was not possible to increase the strength of the material by stretching. PET/PEN blend resins are more easily crystallized by stretch heat‐setting than are PET/PEN copolymer resins. It was understood that this is because residual PET, which has not undergone transesterification, contributes to crystallization. However, because transesterification reduces crystallinity, the heat‐set density of blends did not increase as significantly as that of pure PET, even in high temperature heat‐setting. Gas permeability showed the same tendency as density. Namely, pure PET showed a substantial decrease in oxygen transmission after high temperature heat‐setting, but the decrease in gas permeability in the blend material was small at heat‐set temperatures of 140°C and higher.     

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     

Crystallization of poly(ethylene terephthalate)/polycarbonate blends. I. Unreinforced systems

The crystallization and transition temperatures of poly(ethylene terephthalate) (PET) in blends with polycarbonate (PC) is considered using thermal analysis. Additives typically used in commercial polyester blends, transesterification inhibitor and antioxidant, are found to enhance the crystallization rate of PET. Differential scanning calorimetry (DSC) reveals two glass transition temperatures in PET/PC blends, consistent with an immiscible blend. Optical microscopy observations are also consistent with an immiscible blend. Small shifts observed in the T_g of each component may be due to interactions between the phases. The degree of crystallinity of PET in PET/PC blends is significantly depressed for high PC contents. Also, in blends with PC content greater than 60 wt %, two distinct crystallization exotherms are observed in dynamic crystallization from the melt. The isothermal crystallization kinetics of PET, PET modified with blend additives, and PET in PET/PC blends have been evaluated using DSC and the data analyzed using the Avrami model. The crystallization of PET in these systems is found to deviate from the Avrami prediction in the later stages of crystallization. Isothermal crystallization data are found to superimpose when plotted as a function of time divided by crystallization half-time. A weighted series Avrami model is found to describe the crystallization of PET and PET/PC blends during all stages of crystallization. © 1996 John Wiley & Sons, Inc.     

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.     

Interrelationship of thermal and mechanical properties of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate)/graphene nanocomposites

In the present work, attempts were made to investigate the thermal and mechanical properties of melt‐processed poly(ethylene terephthalate) (PET)/poly(ethylene 2,6‐naphthalate) (PEN) blends and its nanocomposites containing graphene by using differential scanning calorimetry and tensile test experimenting. The results showed that crystallinity, which depends on a blend ratio, completely disappeared in a composition of 50/50. By introducing graphene to PET, even in low concentrations, the crystallinity of samples increased, while the nanocomposite of PEN indicated reverse behavior, and the crystallinity was reduced by adding graphene. In the case of PET‐rich (75/25) nanocomposite blends, by increasing the nano content in the blend, the crystallinity of the samples was enhanced. This behavior was attributed to the nucleating effect of graphene particles in the samples. From the results of mechanical experiments, it was found in PET‐rich blends that by increasing the PEN/PET ratio, the modulus of samples decreased, whereas in the case of PEN‐rich blends, a slight increment of modulus is seen as a result of the increment of the PEN/PET ratio. The two contradicting behaviors were attributed to the reduction of crystallinity of PET‐rich blends by enhancement of PEN/PET ratio and the rigid structure of PEN chains in PEN‐rich blends. Unlike the different modulus change of PET‐rich and PEN‐rich blends, the nanocomposites of these blends similarly indicated an increment of modulus and characteristics of rigid materials by increasing the nano content. Furthermore, the same behavior was detected in nanocomposites of each polymer (PET and PEN nanocomposites). The alteration from ductile to rigid conduction was related to the impedance in the role of graphene plates against the flexibility of polymer chains and high values of graphene modulus. J. VINYL ADDIT. TECHNOL., 23:210–218, 2017. © 2015 Society of Plastics Engineers     

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     

Nonisothermal crystallization kinetics of poly(ethylene terephthalate) and poly(methyl methacrylate) blends

The nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) and poly(methyl methacrylate) (PMMA) blends were studied. Four compositions of the blends [PET 25/PMMA 75, PET 50/PMMA 50, PET 75/PMMA 25, and PET 90/PMMA 10 (w/w)] were melt‐blended for 1 h in a batch reactor at 275°C. Crystallization peaks of virgin PET and the four blends were obtained at cooling rates of 1°C, 2.5°C, 5°C, 10°C, 20°C, and 30°C/min, using a differential scanning calorimeter (DSC). A modified Avrami equation was used to analyze the nonisothermal data obtained. The Avrami parameters n, which denotes the nature of the crystal growth, and Z_t, which represents the rate of crystallization, were evaluated for the four blends. The crystallization half‐life (t_½) and maximum crystallization (t_max) times also were evaluated. The four blends and virgin polymers were characterized using a thermogravimetric analyzer (TGA), a wide‐angle X‐ray diffraction unit (WAXD), and a scanning electron microscope (SEM). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3565–3571, 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     

Crystallization kinetics and crystalline morphology of poly(ethylene naphthalate) and poly(ethylene terephthalate‐co‐bibenzoate)

Copolymers of ethylene glycol with 4,4′‐bibenzoic acid and terephthalic acid are known to crystallize rapidly to surprisingly high levels of crystallinity. To understand this unusual behavior, the isothermal crystallization of poly(ethylene bibenzoate‐co‐terephthalate) in the molar ratio 55:45 (PETBB55) was studied. Poly(ethylene naphthalate) (PEN) was included in the study for comparison. The kinetics of isothermal crystallization from the melt and from the amorphous glass was determined using differential thermal analysis. The results were correlated with the crystalline morphology as observed with atomic force microscopy (AFM). Crystallization of PEN exhibited similar kinetics and spherulitic morphology regardless of whether it was cooled from the melt or heated from the glass to the crystallization temperature. The Avrami coefficient was close to 3 for heterogeneous nucleation with 3‐dimensional crystal growth. The copolymer PETBB55 crystallized much faster than did PEN and demonstrated different crystallization habits from the melt and from the glass. From the melt, PETBB55 crystallized in the “normal” way with spherulitic growth and an Avrami coefficient of 3. However, crystallization from the glass produced a granular crystalline morphology with an Avrami coefficient of 2. A quasi‐ordered melt state, close to liquid crystalline but lacking the order of a recognizable mesophase, was proposed to explain the unusual crystallization characteristics of PETBB55. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 98–115, 2002     

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

The transesterification reaction of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends during melt‐mixing was studied as a function of blending temperature, blending time, blend composition, processing equipment, and different grades of poly(ethylene terephthalate) and poly(ethylene 2,6‐naphthalate). Results show that the major factors controlling the reaction are the temperature and time of blending. Efficiency of mixing also plays an important role in transesterification. The reaction kinetics can be modeled using a second‐order direct ester–ester interchange reaction. The rate constant (k) was found to have a minimum value at an intermediate PEN content and the activation energy of the rate constant was calculated to be 140 kJ/mol. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2422–2436, 2001     

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.     

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     

Properties of poly(ethylene terephthalate)–poly(ethylene naphthalene 2,6‐dicarboxylate) blends with montmorillonite clay

The production and properties of blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) with three modified clays are reported. Octadecylammonium chloride and maleic anhydride (MAH) are used to modify the surface of the montmorillonite–Na⁺ clay particles (clay–Na⁺) to produce clay–C18 and clay–MAH, respectively, before they are mixed with the PET/PEN system. The transesterification degree, hydrophobicity and the effect of the clays on the mechanical, rheological and thermal properties are analysed. The PET–PEN/clay–C18 system does not show any improvements in the mechanical properties, which is attributed to poor exfoliation. On the other hand, in the PET–PEN/clay–MAH blends, the modified clay restricts crystallization of the matrix, as evidenced in the low value of the crystallization enthalpy. The process‐induced PET–PEN transesterification reaction is affected by the clay particles. Clay–C18 induces the largest proportion of naphthalate–ethylene–terephthalate (NET) blocks, as opposed to clay–Na⁺ which renders the lowest proportion. The clay readily incorporates in the bulk polymer, but receding contact‐angle measurements reveal a small influence of the particles on the surface properties of the sample. The clay–Na⁺ blend shows a predominant solid‐like behaviour, as evidenced by the magnitude of the storage modulus in the low‐frequency range, which reflects a high entanglement density and a substantial degree of polymer–particle interactions. Copyright © 2005 Society of Chemical Industry     

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.     

Morphology and barrier mechanism of biaxially oriented poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

To improve the barrier properties of poly(ethylene terephthalate) (PET), PET/poly(ethylene 2,6‐naphthalate) (PEN) blends with different concentrations of PEN were prepared and were then processed into biaxially oriented PET/PEN films. The air permeability of bioriented films of pure PET, pure PEN, and PET/PEN blends were tested by the differential pressure method. The morphology of the blends was studied by scanning electron microscopy (SEM) observation of the impact fracture surfaces of extruded PET/PEN samples, and the morphology of the films was also investigated by SEM. The results of the study indicated that PEN could effectively improve the barrier properties of PET, and the barrier properties of the PET/PEN blends improved with increasing PEN concentration. When the PEN concentration was equal to or less than 30%, as in this study, the PET/PEN blends were phase‐separated; that is, PET formed the continuous phase, whereas PEN formed a dispersed phase of particles, and the interface was firmly integrated because of transesterification. After the PET/PEN blends were bioriented, the PET matrix contained a PEN microstructure consisting of parallel and extended, separate layers. This multilayer microstructure was characterized by microcontinuity, which resulted in improved barrier properties because air permeation was delayed as the air had to detour around the PEN layer structure. At a constant PEN concentration, the more extended the PEN layers were, the better the barrier properties were of the PET/PEN blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1309–1316, 2006     

Isothermal crystallization kinetics and spherulite morphologies of poly(lactic acid)/ethylene acrylate copolymer blends

Isothermal crystallization kinetics and spherulite morphologies of partially immiscible blends of poly(lactic acid) (PLA) and ethylene acrylate copolymer (EAC) were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy. The DSC data obtained was analyzed using the Avrami equation. Crystallization kinetics of PLA from the melt was strongly influenced by the blend composition and the crystallization temperature. At a given crystallization temperature, the overall crystallization rate value was greater in the blends than in PLA suggesting that the presence of EAC enhanced crystallization of PLA. Polarized optical micrographs showed that the crystallization of PLA initially took place at the PLA/EAC interface. At high EAC content (>1 wt %), EAC domains acted as hindrance to crystallization reducing the overall crystallization rate of PLA in the blends. Based on the DSC analysis, the crystallization rate was maximum when PLA blend with 1 wt % EAC was isothermally crystallized at 103 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45487.