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1.
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 Tg, Tm and Tc (crystallization temperature), respectively, are observed from DSC as well as single Tg 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.  相似文献   

2.
Poly(ethylene glycol) (PEG) and end‐capped poly(ethylene glycol) (poly(ethylene glycol) dimethyl ether (PEGDME)) of number average molecular weight 1000 g mol?1 was melt blended with poly(ethylene terephthalate) (PET) oligomer. NMR, DSC and WAXS techniques characterized the structure and morphology of the blends. Both these samples show reduction in Tg and similar crystallization behavior. Solid‐state polymerization (SSP) was performed on these blend samples using Sb2O3 as catalyst under reduced pressure at temperatures below the melting point of the samples. Inherent viscosity data indicate that for the blend sample with PEG there is enhancement of SSP rate, while for the sample with PEGDME the SSP rate is suppressed. NMR data showed that PEG is incorporated into the PET chain, while PEGDME does not react with PET. Copyright © 2005 Society of Chemical Industry  相似文献   

3.
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  相似文献   

4.
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 Tg 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  相似文献   

5.
The miscibility and melting behavior of binary crystalline blends of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) have been investigated with differential scanning calorimetry and scanning electron microscope. The blends exhibit a single composition‐dependent glass transition temperature (Tg) and the measured Tg fit well with the predicted Tg value by the Fox equation and Gordon‐Taylor equation. In addition to that, a single composition‐dependent cold crystallization temperature (Tcc) value can be observed and it decreases nearly linearly with the low Tg component, PTT, which can also be taken as a valid supportive evidence for miscibility. The SEM graphs showed complete homogeneity in the fractured surfaces of the quenched PET/PTT blends, which provided morphology evidence of a total miscibility of PET/PTT blend in amorphous state at all compositions. The polymer–polymer interaction parameter, χ12, calculated from equilibrium melting temperature depression of the PET component was ?0.1634, revealing miscibility of PET/PTT blends in the melting state. The melting crystallization temperature (Tmc) of the blends decreased with an increase of the minor component and the 50/50 sample showed the lowest Tmc value, which is also related to its miscible nature in the melting state. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

6.
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 (Ti) were determined to draw useful information about the overall thermal stability of the studied compounds. Also, the glass transition temperature (Tg) 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  相似文献   

7.
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 Tg 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.  相似文献   

8.
The crystallization behavior of two molecular weight poly(ethylene oxide)s (PEO) and their blends with the block copolymer poly(2‐vinyl pyridine)‐b‐poly(ethylene oxide) (P2VP‐b‐PEO) was investigated by polarized optical microscopy, thermogravimetric analysis, differential scanning calorimetry, and atomic force microscopy (AFM). A sharp decreasing of the spherulite growth rate was observed with the increasing of the copolymer content in the blend. The addition of P2VP‐b‐PEO to PEO increases the degradation temperature becoming the thermal stability of the blend very similar to that of the block copolymer P2VP‐b‐PEO. Glass transition temperatures, Tg, for PEO/P2VP‐b‐PEO blends were intermediate between those of the pure components and the value increased as the content of PEO homopolymer decreased in the blend. AFM images showed spherulites with lamellar crystal morphology for the homopolymer PEO. Lamellar crystal morphology with sheaf‐like lamellar arrangement was observed for 80 wt% PEO(200M) and a lamellar crystal morphology with grain aggregation was observed for 50 and 20 wt% blends. The isothermal crystallization kinetics of PEO was progressively retarded as the copolymer content in the blend increased, since the copolymer hinders the molecular mobility in the miscible amorphous phase. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers  相似文献   

9.
Blends composed of poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) were melt-mixed in a Brabender cam mixer at different mixing speeds. The glass transition (Tg) and the crystallization behavior of the blends from glassy state were studied using DSC. It was found that although the blends had the same composition and exhibited the similar Tg, their properties of crystallization could be different; some exhibited a single crystallization peak and some exhibited multiple crystallization peaks depending upon experimental conditions. Results indicated that the behavior of crystallization from glassy state were influenced by entanglement and transesterification of chains. The crystallization time values were obtained over a wide range of crystallization temperature. From curve fitting, the crystallization time values and the temperature, at which the crystallization rate reaches the maximum, were found.  相似文献   

10.
Summary Miscibility of blends of poly(ether imide) (PEI) and poly(ethylene terephthalate) (PET) were studied by differential scanning calorimetry (DSC). Single and composition-dependent Tg's are observed over the entire composition range, indicating that the blends are miscible in the amorphous region. The overall crystallization rate of PET in the blends decreased with increasing the PEI content. The interaction energy density B, which was calculated from the melting point depression of the blends using Nishi-Wang equation, was-5.5 cal/cm3.  相似文献   

11.
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 Tg 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  相似文献   

12.
Blends based on recycled high density polyethylene (R‐HDPE) and recycled poly(ethylene terephthalate) (R‐PET) were made through reactive extrusion. The effects of maleated polyethylene (PE‐g‐MA), triblock copolymer of styrene and ethylene/butylene (SEBS), and 4,4′‐methylenedi(phenyl isocyanate) (MDI) on blend properties were studied. The 2% PE‐g‐MA improved the compatibility of R‐HDPE and R‐PET in all blends toughened by SEBS. For the R‐HDPE/R‐PET (70/30 w/w) blend toughened by SEBS, the dispersed PET domain size was significantly reduced with use of 2% PE‐g‐MA, and the impact strength of the resultant blend doubled. For blends with R‐PET matrix, all strengths were improved by adding MDI through extending the PET molecular chains. The crystalline behaviors of R‐HDPE and R‐PET in one‐phase rich systems influenced each other. The addition of PE‐g‐MA and SEBS consistently reduced the crystalline level (χc) of either the R‐PET or the R‐HDPE phase and lowered the crystallization peak temperature (Tc) of R‐PET. Further addition of MDI did not influence R‐HDPE crystallization behavior but lowered the χc of R‐PET in R‐PET rich blends. The thermal stability of R‐HDPE/R‐PET 70/30 and 50/50 (w/w) blends were improved by chain‐extension when 0.5% MDI was added. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

13.
Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10–40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200–7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (Tm), cold crystallization and glass transition (Tg) decreased with the copolymerization. Tm depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. Tg was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.  相似文献   

14.
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  相似文献   

15.
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 Tgs. The lower Tg was ∼72 °C, independent of the blend ratio. In contrast, the higher Tg increased with increasing PEN content. Thus, the coextrusion was carried out around the higher Tg 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.  相似文献   

16.
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  相似文献   

17.
The compatibility of ternary blends of poly(ethylene naphthalate)/poly(pentamethylene terephthalate)/poly(ether imide) (PEN/PPT/PEI) was studied by examining the transesterification of PEN and PPT. ENPT copolymers were formed in situ as compatibilizers between PPT and PEI components in ternary blends. Differential scanning calorimetric (DSC) results for ternary blends showed the immiscibility of PEN/PPT/PEI, but ternary blends of all compositions were phase‐homogeneous after heat treatment at 300°C for more than 60 min. Annealing samples at 300°C yielded amorphous blends with a clear, single glass transition temperature (Tg), as the final state. Additionally, ENPT copolymer improved the compatibility of ENPT/PPT/PEI blends, yielding a homogeneous phase in the ENPT‐rich compositions. The morphology of the ENPT/PPT/PEI blends was altered from heterogeneous to homogeneous by controlling the concentration of PPT in the ENPT copolymers as well as the concentration of the ENPT copolymers. Moreover, a homogeneous phase with a clear Tg was observed when the concentration of PPT in the ENPT copolymer fell to 70 wt% in the ENPT/PEI = 50/50 blends. Experimental results indicate how the concentration of PPT in the ENPT copolymer affects miscibility in the ENPT/PEI blends. POLYM. ENG. SCI. 46:337–343, 2006. © 2006 Society of Plastics Engineers  相似文献   

18.
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  相似文献   

19.
Compatibilized blends of poly(ethylene terephthalate (PET) with an aromatic polyamide such as poly(m‐xylylene adipamide) (MXD6) have good transparency (T) because the constituent refractive indices (RIs) match closely. However, haziness is observed when the blends are stretched. This study demonstrated that stretching imparted a greater RI anisotropy to PET than to the aromatic polyamide. The resulting RI mismatch was responsible for the loss in T. Analysis of the strain‐dependent birefringence revealed that different molecular deformation models described the intrinsic birefringence of the PET and aromatic polyamides. Hydrogen bonding of the polyamide may have been responsible for the difference. On the basis of these results, three approaches for improving T of stretched PET blends were attempted. Blends with a lower molecular weight MXD6 exhibited slightly higher T after stretching; however, they did not compare with stretched PET. Increasing the amount of compatibilizer reduced the particle size; however, the dimension of even the smallest particles exceeded the quarter wavelength after biaxial stretching transformed the spherical particles into platelets. Copolyamides based on MXD6 that incorporated isophthalate were designed to increase the RI of the polyamide and thereby reduce the RI mismatch with stretched PET. Unexpectedly, the poor T of stretched copolyamide blends was attributed to the high glass‐transition temperature of the copolyamide, which hampered the molecular orientation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 225–235, 2006  相似文献   

20.
The nucleation of poly(ethylene terephthalate) (PET) by codiols and olefinic segments was studied. The codiols 1,5‐pentanediol, 1,8‐octanediol, 2,5‐hexanediol, and 1,3‐dihydroxymethyl benzene were copolymerized into PET in a concentration range of 0–10 mol %. The melting (Tm), crystallization (Tc), and glass‐transition (Tg) temperatures were studied. These codiols were found to be able to nucleate PET at low concentrations, probably by lowering the surface free energy of the chain fold. However, the codiols also disturbed the structural order of the polymer, resulting in a decrease in both the Tm and Tc values. The optimum codiol concentration was found to be at around 1 mol %, which is lower than previously reported. A diamide segment N,N′‐bis(p‐carbo‐methoxybenzoyl)ethanediamine (T2T) was found to be a more effective nucleator than the codiols; however, no synergy was observed between the nucleating effect of the diamide segment T2T and that of the codiol. An olefinic diol (C36‐diol) with a molecular weight of 540 g/mol was also copolymerized into PET in a concentration range of 0–21 wt %. Only one Tg was observed in the resulting copolymers, suggesting that the amorphous phases of PET and the C36‐diol are miscible. The main effect of incorporating the C36‐diol into PET was the lowering of the Tg; thus, the C36‐diol is an internal plastifier for PET. The C36‐diol had little effect on the Tm value; however, the Tc value actually increased in the 11.5 wt % copolymer. As the Tg decreased and the Tc increased, the crystallization window also increased and thereby the likelihood of crystallization. Therefore, the thermally stable C36‐diol appears to be an interesting compound that may be useful in improving the crystallization of PET. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2676–2682, 2001  相似文献   

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