Blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Commercial grade poly(ethylene terephthalate), (PET, intrinsic viscosity = 0.80 dL/g) and poly(butylene terephthalate), (PBT, intrinsic viscosity = 1.00 dL/g) were melt blended over the entire composition range using a counterrotating twin‐screw extruder. The mechanical, thermal, electrical, and rheological properties of the blends were studied. All of the blends showed higher impact properties than that of PET or PBT. The 50:50 blend composition exhibited the highest impact value. Other mechanical properties also showed similar trends for blends of this composition. The addition of PBT increased the processability of PET. Differential scanning calorimetry data showed the presence of both phases. For all blends, only a single glass‐transition temperature was observed. The melting characteristics of one phase were influenced by the presence of the other. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 75–82, 2005     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

Collagen immobilization on poly(ethylene terephthalate) and polyurethane films after UV functionalization

An attractive alternative method to add new functionalities such as biocompatibility due to the micro- and nanoscaled modification of surfaces is offered by UV-modified polymers. The aim of this study was to evaluate the effect of the UV light functionalization on two polymers, poly(ethylene terephthalate) (PET) and polyurethane (PU) films, by means of atomic force microscopy (AFM), Fourier transform infrared–attenuated total reflectance (FTIR–ATR), and contact angle measurements. Thus, the UV-irradiation activates the polymers surface by breaking some chemical bonds and generation of new functional groups on the surface. This process can be controlled by the irradiation time. The topography provides the formation of superposed ‘nap’ and ‘wall-type’ structures on both untreated and treated samples. The surface parameters were found to depend on the polymer films before and after irradiation. The immobilization of collagen on PET surface was confirmed by X-ray photoelectron spectroscopy measurements and for PU surface was proved by FTIR–ATR. First technique suggests an increase of the nitrogen content at longer UV exposure time, and the second one reveals the appearance of the protein Amide I band. Supplementary, AFM measurements clearly revealed the presence of collagen attached on the polymer surface. Thus, these new UV-irradiated polymers are promising materials in our further attempts to obtain new biofunctionalized surfaces.     

Surface modification of poly(ethylene terephthalate) film by coating with poly(ethylene glycol)‐grafted polystyrene

The poly(ethylene glycol) (PEG)‐grafted styrene (St) copolymer, which was formed as a nanosphere, was used as an agent to modify the surface of poly(ethylene terephthalate) (PET) film. The graft copolymer was dissolved into chloroform and coated onto the PET film by dip–coating method. The coated amount depends on the content ratios of PEG and St, the solution concentration, and the coating cycles. The graft copolymers having a low molecular weight of PEG‐ or St‐rich content was fairly stable on washing in sodium dodecyl sulfate (SDS) aqueous solution. It was confirmed that the PET surface easily altered its surface property by the coating of the graft copolymers. The contact angles of the films coated with the graft copolymers were very high (ca. 105–120°). The coated film has good antistatic electric property, which agreed with PEG content. The best condition of coating is a one‐cycle coating of 1% (w/v) graft copolymer solution. The coated surface had water‐repellency and antistatic electric property at the same time. The graft copolymer consisted of a PEG macromonomer; St was successfully coated onto PET surfaces, and the desirable properties of both of PEG macromonomer and PSt were exhibited as a novel function of the coated PE film. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1524–1530, 1999     

Modification of poly(ethylene terephthalate) surface with attached dextran macromolecules

BACKGROUND: Peroxidation of a poly(ethylene terephthalate) (PET) surface clears the path to the formation of biospecific polymeric layers on it. The goal of this work was the modification of a PET surface with oligoperoxides with further grafting of dextran macromolecules to this peroxidated surface. RESULTS: Novel oligoperoxides with a good affinity to PET were synthesized. They are capable of attaching to the PET surface, due to the decomposition of peroxide groups via the formation of free radicals. The alterations in surface energy and its components as a result of surface modification as well as changes in topography of the PET surface were determined. The degree of modification of the PET surface can reach 68% and depends on the following: the method of oligoperoxide and dextran deposition; the concentration of both oligoperoxide and dextran in the initial solution; and the temperature at which the modification is carried out. CONCLUSION: A new method of PET surface activation has been developed. The attachment of dextran macromolecules to modified PET surfaces is confirmed. Copyright © 2009 Society of Chemical Industry     

Morphology and crystallization of poly(ethylene terephthalate)

The melting behaviour and the morphology of poly(ethylene terephthalate) crystallized from the melt are reported. In general, dual or triple melting endotherms are seen, and single endotherms are seen when the samples are crystallized above 215°C for long times. The location of the uppermost endotherm was found to be constant below T_c = 230°C, and above that temperature the location depends on T_c. Therefore, we have shown that samples of PET which are crystallized above T_c = 230°C contain perfect crystals only; below T_c = 230°C, they contain perfect and imperfect crystals. Scanning electron microscopy showed that the perfect crystals are the dominant lamellae in the spherulitic structure, while the imperfect crystals are the subsidiary lamellae in the spherulitic structure, The amorphous regions are located between individual lamellae.     

Surface nature of UV deterioration in properties of solid poly(ethylene terephthalate)

We investigated the changes in the molecular weight and also in the mechanical properties with the distance to the exposed surface of the irradiated stacked poly(ethylene terephthalate) (PET) film samples. A relation between the molecular weight and the mechanical properties of the irradiated PET was established. The relation demonstrates that the decrease in molecular weight is one of the main origins causing the deterioration in the mechanical properties. The photodegradation process developing in PET was quantitatively studied by investigating the degradation kinetics of stacked PET film samples. Our results show that the strongest degradation takes place at the exposed surface, and the degradation rate decreases with increasing the distance. This further implies that the capability to bear a tensile stress in the area near the exposed surface is much lower than that in bulk. Therefore, irradiated PET may be fractured in a lower stress. These results indicate the surface nature of ultraviolet deterioration in the physical properties of PET. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 705–714, 1998     

Comparative studies on surface modification of poly(ethylene terephthalate) by remote and direct argon plasmas

Surface modification of poly(ethylene terephthalate) (PET) film by an argon (Ar) plasma was investigated as a function of the distance from the Ar plasma zone. Changes in distance between the PET film and the Ar plasma zone had a strong influence on the surface modification of the film. The direct Ar plasma treatment (distance between the PET film and Ar plasma zone = 0 cm) was effective in hydrophilic surface modification, but heavy etching reactions occurred during the modification. On the other hand, the remote Ar plasma treatment (distance between the PET film and Ar plasma zone = 80 cm) modified the PET film surfaces to be hydrophilic without heavy etching reactions, although the hydrophilicity of the PET was lower than that by the direct Ar plasma. The remote Ar plasma treatment was distinguished from the direct Ar plasma treatment from the viewpoint of degradation reactions. The remote Ar plasma treatment rather than the direct Ar plasma treatment was an adequate procedure for surface modification and caused less polymer degradation on the film surface. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 808–815, 2001     

A photochemical method for immobilization of azidated dextran onto aminated poly(ethylene terephthalate) surfaces

BACKGROUND: Dextran, a bacterial polysaccharide, has been reported to be as good as poly(ethylene glycol) in its protein‐rejecting and cell‐repelling abilities. In addition, the multivalent nature of dextran is advantageous for surface grafting of biologically active molecules. We report here a method to photochemically bind dextran hydrogel films to aminated poly(ethylene terephthalate) (PET) surfaces in aqueous media using a heterobifunctional crosslinker, 4‐azidobenzoic acid. In order to achieve this, dextran was first functionalized with the crosslinker using carbodiimide chemistry followed by photo‐crosslinking and immobilization onto the nucleophile‐rich aminated PET surfaces. RESULTS: The presence of the immobilized dextran on PET was verified by attenuated total‐reflection Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy and contact angle measurements. The grafted surface was highly hydrophilic due to the heavily hydrated polysaccharide network on the surface as demonstrated by the near zero water contact angle. CONCLUSION: A photochemical method for surface immobilization of dextran onto aminated PET using aryl azide chemistry is a facile technique to generate highly hydrophilic and more hemocompatible surfaces. The aryl nitrenes generated by photolysis produce a metastable, electron‐deficient intermediate, azacycloheptatetraene, which is believed to be responsible for the simultaneous crosslinking of dextran and its immobilization onto the aminated PET surface. The aryl azide chemistry reported here for dextran could be useful as a versatile technique for surface modification of other nucleophile‐rich polymers to create dextran‐ or similar polysaccharide‐immobilized surfaces. Copyright © 2007 Society of Chemical Industry     

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 influence of surface modification on the structure and properties of a zinc oxide‐filled poly(ethylene terephthalate)

Hydrophobic zinc oxide (ZnO) nanoparticles were successfully prepared by a one‐step precipitation reaction in an aqueous solution of zinc sulfate and sodium hydroxide with stearic acid as the modifying agent. Poly(ethylene terephthalate) (PET)/ZnO nanocomposites were prepared by further in situ polymerization of purified terephthalic acid, ethylene glycol and the ZnO nanoparticles. The surface modification of ZnO and the microstructure and properties of the nanocomposites were investigated using relative contact angle measurements, Fourier transform infrared spectroscopy, X‐ray diffraction, transmission and scanning electron microscopies, thermogravimetric analysis and differential scanning calorimetry. Measurements of relative contact angle indicated that the surface‐treated ZnO was hydrophobic. Compared to the nanocomposite filled with unmodified ZnO, a significant improvement in thermal stability and crystallinity was observed with the addition of 2 wt% surface‐treated ZnO. The experimental results also suggested that the properties of the nanocomposites were correlated with the dispersion of ZnO in PET and the interfacial interactions between ZnO and PET matrix. © 2012 Society of Chemical Industry     

Effect of poly(ethylene glycol) on the solid‐state polymerization of poly(ethylene terephthalate)

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 T_g 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     

Thermal crosslinking of collagen immobilized on poly(acrylic acid) grafted poly(ethylene terephthalate) films

Graft polymerization of acrylic acid onto plasma‐treated poly(ethylene terephthalate) (PET) films was used to prepare surfaces suitable for collagen immobilization by dip‐coating. Such surfaces could be used as matrices for smooth muscle cell cultures in tissue engineering. Contact angle measurements showed that plasma‐treated and grafted PET films undergo considerable surface reorganization during storage under ambient conditions. However, after collagen immobilization the contact angle remained relatively stable. The amount of collagen initially attached to the film surface increased with increasing poly(acrylic acid) graft density, but subsequent washing in water led to significant collagen loss. This loss could nevertheless be substantially reduced by thermal crosslinking of the collagen in the range 110–130 °C. Atomic force microscopy (AFM) observations suggested that the washed crosslinked collagen has a very similar structure to that of the un‐crosslinked collagen. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1874–1880, 2002     

聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)等温结晶行为研究

以对苯二甲酸(PTA)、乙二醇(EG)、异山梨醇(ISB)为原料,通过直接熔融缩聚法合成聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)(PEIT)共聚酯。利用差示扫描量热法(DSC)研究了共聚酯的结晶行为,采用Avrami方程分析了共聚酯的等温结晶动力学。结果表明,PEIT共聚酯结晶行为受共聚组成和结晶温度影响。随着ISB用量的增加或结晶温度的降低,共聚酯半结晶周期t1/2增加、结晶速率变慢;ISB摩尔分数超过20%,共聚酯无法结晶。     

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     

Swollen-state polymerization of poly(ethylene terephthalate) in fibre form

The swollen-state polymerization of poly(ethylene terephthalate) in fibre form was performed in hydrogenated terphenyl as the swelling solvent. Ultra-high-molecular-weight poly(ethylene terephthalate) (CHMW-PET) fibre with an intrinsic viscosity of 3–4dl g⁻¹ (M_n = 2–3 × 10⁵) was obtained. The polymerization rate of as-spun PET fibres in the swollen state was greater than that of PET granules in the swollen state. It was clarified that the polymerization rate was related to the chain mobility of the starting materials. The chain mobility was influenced by various conditions, such as changing rigidity of the segments during copolymerization, the chain orientation of the starting fibre before swollen-state polymerization and the temperature of pretreatment with the solvent. Pretreatment with solvent before polymerization was effective in increasing the chain mobility. The relation between chain mobility and polymerization rate was examined by wide-angle X-ray diffraction, density, differential scanning calorimetry, solvent content and viscoelastic measurements. Undrawn UHMW-PET fibres could be drawn 10 times or more by the zone drawing technique in spite of their high crystallinity, and the drawn fibre showed high tensile strength (12 g d⁻¹) and high modulus (240 g d⁻¹).     

Transesterification in poly(ethylene terephthalate) and poly(ethylene naphthalate 2,6-dicarboxylate) blends: model compounds study

Kinetics of transesterification reaction in poly(ethylene terephthalate)-poly(ethylene naphthalate 2,6-dicarboxylate), PET-PEN, blends resulting from melt processing was simulated using model compounds of ethylene dibenzoate (BEB) and ethylene dinaphthoate (NEN). The exchange reaction between BEB and NEN was followed by ¹H NMR spectroscopy using signals from the aliphatic protons of ethylene glycol moieties at 4.66 and 4.78 ppm, respectively. The first-order kinetics was established under pseudo-first-order conditions for both reactants. Thus, the overall transesterification reaction was second order reversible. The reversibility was confirmed experimentally by heating a mixed sequence of 1-benzoate 2-naphthoate ethylene (BEN) under similar conditions. Both forward reaction of the equimolar amounts of the reagents and reverse reaction came to equilibrium at the same molar ratio of the reactants and reaction products of roughly 0.25:0.50:0.25 for BEB, BEN, and NEN, respectively. The rate equation for the transesterification reaction in the model system was modified using half-concentration of BEN, which is the only effective in the intermolecular exchange. Direct ester-ester exchange was deduced as a prevailing mechanism for the transesterification reaction under the conditions studied, and the values of equilibrium and rate constants, as well as other basic thermodynamic and kinetic parameters were determined. The use of Zn(OAc)₂ as a catalyst resulted in a significant decrease in the activation enthalpy of transesterification, which might be due to the partial switch of the reaction mechanism from primarily pseudo-homolytic to more heterolytic where Zn^II acts as a Lewis base which binds to the ester carbonyl oxygen.     

Biodegradability of poly(ethylene terephthalate) copolymers with poly(ethylene glycol)s and poly(tetramethylene glycol)

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 (T_m), cold crystallization and glass transition (T_g) decreased with the copolymerization. T_m depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. T_g 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.     

Modeling of solid-state polymerization of poly(ethylene terephthalate)

A mathematical model for solid-state polymerization of poly(ethylene terephthalate) was developed. The effects of temperature and chain entanglement on chain mobility were considered to estimate the rate constants of chemical reactions. The diffusivities of volatile byproducts could be determined using the free volume theory.^13,14 The model predictions were validated with experimental data reported in the literature. In addition, assuming that the concentration profiles of volatile byproducts in spherical particles are described by a sinusoidal function, the mass transfer rate of the byproducts at a given time could be derived as an ordinary differential equation that can be easily treated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:837–846, 1998     

Volatile products of poly(ethylene terephthalate) thermal degradation in nitrogen atmosphere

Thermal degradation of PET was studied in a nitrogen atmosphere at 200–700°C. The experiments were carried out in a tubular furnace under isothermal conditions. The volatile substances evolved from PET were identified and quantified. Weight losses of PET during the thermal degradation in different temperatures were determined. The results are presented on plots as a function of the degradation temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1894–1901, 2000