Visible dichroism of polypropylene–disperse dye system at high temperatures

The dichroism of polypropylene film dyed with C. I. Disperse Yellow 7 was investigated at various temperatures up to 160°C. The dichroic value D drops as the temperature is raised. So long as the amorphous structure does not change irreversibly, D changes reversibly with temperature. The experimental results agree qualitatively with those obtained on poly(ethylene terephthalate) in our previous paper, although the effect of temperature on the extent of the reversible change in D is larger in PP than in PET. The plot of D versus temperature exhibits breaks at 40°–50°C (T₀), 70°–80°C (T₁), and 115°–120°C (T₃). These temperatures agree with the transition points of polypropylene in the literature. From the change in the intrinsic dichroism D₀ with temperature, it is concluded that the decrease in D at high temperatures is due to the drop of D₀ caused by the disorientation of dye molecules in the amorphous region, while the amorphous polymer chain is not disoriented. Such a conclusion is supported by the fact that Δn of a heat-set specimen is kept constant during heating, in contrast to D.     

Dichroism of poly(ethylene terephthalate)-disperse dye system

As an approach to the basic study on the orientation behavior of amorphous region, the dichroic orientation factor, D, of poly(ethylene terephthalate), PET, fiber or film dyed with disperse dyes was investigated in relation to Δn, birefringence of the crystalline and amorphous regions, and Δn_a, birefringence of the amorphous region. It was found that D versus Δn plot belonged to a linear relationship passing through the origin but breaking slightly toward the D axis at Δn ? 0.14, while D versus Δn_a plot was expressed by a straight line passing similarly through the origin but with no break. D₀, the value of D at the ideal parallel orientation, was obtained by extrapolating the latter plot of the samples stretched with no relaxation: 1.00 and 0.73 for the PET–C.I. Disperse Yellow 7 and PET–C.I. Disperse Red 17 systems respectively. When the sample had been relaxed, the D versus Δn_a was also linear; however, D₀'s obtained were smaller than the above mentioned respective values. Even in these cases D for Disperse Yellow 7 versus the corresponding D for Disperse Red 17 belonged to a linear relationship with the slop 1:0.73. As the result it was concluded that the transition moment of molecule of C.I. Disperse Yellow 7 coincided with the molecular axis and the dye molecule combined parallel to PET chain, while as to C.I. Disperse Red 17 any definite conclusion could not be determined. However, in the both cases the mode of combination of dye molecules with PET is definite and kept unchanged during stretching and heating.     

Mechanical compatibilization of high density polyethylene–poly(ethylene terephthalate) blends

Blends of high density polyethylene (HDPE) and poly(ethylene terephthalate) (PET) exhibit extremely poor mechanical properties owing to the incompatibility of these two polymers. Such blends, however, would result from the reprocessing of certain carbonated beverage bottles. Addition of small amounts of a commercially available triblock copolymer greatly improved the ductility of these incompatible blends, whereas addition of an ethylene–propylene elastomer did not. The results are discussed in terms of phase morphology and interfacial adhesion among the various components.     

Dissolution and crystallization behavior of poly(ethylene terephthalate)–diluent mixtures

The solution crystallization kinetics and crystal dissolution behavior of three grades of poly (ethylene terephthalate) in N-methyl–2-pyrrolidinone were studied were using turbidimetric and calorimetric methods. The influence of concentration on the equilibrium dissolution temperature was described using Flory's melting point-composition relationship. The effect of the solvent alkyl group was also investigated. N-ethyl-2-pyrrolidinone was found to be a better solvent than N-ethyl–2-pyrrolidinone or N-cyclohexyl–2-pyrrolidinone for poly (ethylene terephthalate). From the calorimetric experiments, it was determined that two crystallization processes (primary and secondary crystallization) were responsible for the total crystallinity. The primary process dominated the early stages of the crystallization process and accounted for the majority of the final crystallinity for lower polymer concentrations. Based on coherent secondary nucleation theory, the effect of the crystallization temperature on the primary crystallization rate constant was quantified in terms of a temperature coefficient. This temperature coefficient was found to be relatively insensitive to PET concentration, PET structural impurities, and solvent alkyl group. © 1993 John Wiley & Sons, Inc.     

Improving antistatic properties of poly(methylvinylpyridine)–poly(ethylene terephthalate) graft copolymers via alkylation

The alkylation reaction of poly(methylvinylpyridine)–poly(ethylene terephthalate) graft copolymers with different alkylating agents using monochloroacetic acid has proved to be the best as far as degree of alkylation and enhancement in electrical conductivity caused thereby are concerned. Kinetic investigation revealed that alkylation follows a second-order reaction, and the apparent activation energy is 15.23 cal/mole.     

Orientation and crystallization in poly(ethylene terephthalate) during drawing at high temperatures and strain rates

We review some recent research developments on structure development during drawing of poly(ethylene terephthalate) film, and we report a study of constant-load drawing of amorphous PET film at temperatures of 120°C and 132°C, including the effects of redrawing high-temperature drawn film at lower temperature. To permit constant-load drawing at high temperature without inducing crystallization in the undrawn specimen, a drawing instrument was built that permits very rapid heating of the sample, and its operation is described. The initial stage of drawing at high temperatures is characterized by polymer flow where, owing to high rates of molecular relaxation, neither molecular orientation nor crystallization occurs. Strain-rate increases sharply in the course of the deformation, reducing the time available for relaxation, and the chains start to orient at a draw ratio that depends on temperature. Orientation rapidly reaches a saturation level, which is lower at the higher draw temperature. Crystallization onset seems to lag only slightly behind orientation onset because the critical orientation for inducing crystallization is very low at these temperatures. It appears that there is time for crystallization to proceed to pseudo-equilibrium values corresponding to a particular orientation level, which differs from previous results obtained from constant-force drawing at lower temperatures, and possible reasons for this are discussed. In two-stage drawing, where film drawn at 132°C was redrawn along the same axis at 100°C, high draw ratios were obtained despite the high strain rates, and the levels of noncrystalline orientation and crystallinity were similar to the levels expected from single stage drawing at 100°C.     

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

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

Processing–structure–property relationships in poly(ethylene terephthalate) blown film

An investigation was undertaken to establish processing–structure–property relationships in poly(ethylene terephthalate) (PET) blown film. For the study, a commercial grade of PET was used to fabricate the film specimens by means of a tubular film blowing process. In this process, the stretch temperature was accurately controlled by an oven. The annealing treatment of the oriented specimens involved clamping the sample in an aluminum frame and then putting the clamped sample in an oven, controlled at a temperature between the glass transition temperature (70°C) and the melting point (255°C) of PET, for a specified annealing period. The structure of the blown film samples was characterized by density, bulk birefringence, flat plate wide-angle X-ray scattering, and pole figure analysis. The processing variables, namely, takeup ratio, blowup ratio, and stretch temperature were found to significantly affect the bulk birefringence and density of the oriented PET blown film samples. It was found that both the bulk birefringence and density of the specimens increased upon annealing at an elevated temperature. Both the crystalline and amorphous orientation functions were calculated from the data of bulk birefringence, density, and the pole figure analysis. Compared to the amorphous orientation functions, the crystalline orientation functions were found to be relatively insensitive to the processing variables. It was concluded that equibiaxially oriented PET films can be produced via a tubular film blowing process by judiciously controlling the processing and annealing conditions. It has also been observed that the tensile stress-at-break of equibiaxially oriented PET film increases with decreasing stretch temperature and increasing annealing temperature.     

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     

Synthesis of and photodegradation in a series of poly(ethylene terephthalate)–co–4,4′-sulfonyldibenzoate yarns

Phototendering studies of poly(ethylene terephthalate) homopolymer yarn and a series of poly(ethylene terephthalate–co–4, 4′-sulfonyldibenzoate) copolymer yarns have shown that photosensitized degradation occurs more readily in the copolymers than in the homopolymer. A photo-oxidative mechanism involving the second monomer, dibutyl 4, 4′-sulfonyldibenzoate, has been proposed to account for the photosensitization. The photophysical processes in the second monomer, dibutyl 4, 4′-sulfonyldibenzoate, were studied by absorption and luminescence techniques. The lowest excited singlet and triplet in this compound were identified as the ¹(π, π^*) and ₃(π, π^*) states, respectively. The energy levels in the second monomer have been assigned as follows: ¹S₁ ～ 33,000 cm^?1, ¹S₂ ～ 42,000 cm^?1, and ³T₁ ～ 26,000 cm^?1.     

Flame-retardant poly(ethylene terephthalate)

Poly(ethylene terephthalate) containing hexabromobenzene, tricresyl phosphate, or a combination of triphenyl phosphate and hexabromobenzene, pentabromotoluene, or octabromobiphenyl was extruded or spun at 280°C into monofilaments or low-denier yarn, respectively. Only combinations of the phosphorus- and halogen-containing compounds resulted in flame-retardant poly(ethylene terephthalate) systems, without depreciating their degree of luster and color quality. The melting temperature, the reduced viscosity, and the thermal stability above 400°C of these flame-retardant systems were in most cases comparable to those of poly(ethylene terephthalate) itself. Phosphorus-bromine synergism was proposed with flame inhibition occurring mostly in the gas phase.     

Thermal and mechanical behavior of polycarbonate–poly(ethylene terephthalate) blends

Melt blends of polycarbonate and poly(ethylene terephthalate) were formed by continuous extrusion and injection-molded into bars for mechanical testing. Thermal analysis was used to ascertain transitional behavior and the level of PET crystallinity at various points in the fabrication and testing process. The mechanical properties showed little departure from additivity except for the percent elongation at break which was substantially larger for certain blends than expected. Glass transition behavior suggests two amorphous phases for PC rich mixtures and only one mixed phase in the PET rich region. Crystallizability of the PET after the blend was held for prolonged times in the melt state suggests that interchange reactions do not occur to any great extent.     

Enhanced dynamic mechanical and shape‐memory properties of a poly(ethylene terephthalate)–poly(ethylene glycol) copolymer crosslinked by maleic anhydride

Dimethyl terephthalate (DMT) and ethylene glycol (EG) were used for the preparation of poly(ethylene terephthalate) (PET), and poly(ethylene glycol) (PEG) was added as a soft segment to prepare a PET–PEG copolymer with a shape‐memory function. MWs of the PEG used were 200, 400, 600, and 1000 g/mol, and various molar ratios of EG and PEG were tried. Their tensile and shape‐memory properties were compared at various points. The glass‐transition and melting temperatures of PET–PEG copolymers decreased with increasing PEG molecular weight and content. A tensile test showed that the most ideal mechanical properties were obtained when the molar ratio of EG and PEG was set to 80:20 with 200 g/mol of PEG. The shape memory of the copolymer with maleic anhydride (MAH) as a crosslinking agent was also tested in terms of shape retention and shape recovery rate. The amount of MAH added was between 0.5 and 2.5 mol % with respect to DMT, and tensile properties and shape retention and recovery rate generally improved with increasing MAH. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 27–37, 2002     

Conductive fibers based on poly(ethylene terephthalate)–polyaniline composites manufactured by electrochemical polymerization

A novel method of manufacturing composite conductive fibers was developed through electrochemical polymerization with an apparatus consisting of insulating fibers, cotton fabrics as electrolytic solution holders, an electrolytic solution, and planer electrodes. By this method, poly(ethylene terephthalate) (PET) fibers coated with polyaniline (PAN) were prepared readily and yielded PET–PAN composite conductive fibers (PPCFs). The content of PAN in PPCFs increased with an increase in both the aniline concentration in the electrolytic solution and the polymerization voltage, although it did not depend on the load applied to the electrodes. Observations of the PPCF surface by scanning electron microscopy confirmed that the formation processes of PPCFs could be divided into three steps: (1) fine (nanometer‐size) granular PAN was generated from the anode and adsorbed onto the PET fiber surface, (2) the size of the granular PAN increased up to about 90 nm in a short time, and (3) the granular PAN was linked together to form networks. The conductivity of PPCFs increased with an increasing content of PAN networks. The surface resistance of the PPCF fabric was about 3 × 10⁵ Ω/□ at a PAN content of approximately 2 wt %. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1073–1078, 2003     

Powdered poly(ethylene terephthalate)

The influence of the conditions of preparation on the properties of powdered poly(ethylene terephthalate) was followed from the point of view of its specific surface. The powdered poly(ethylene terephthalate) prepared by reprecipitation from the melt of 6-caprolactam has a porous and structured surface, and consequently, also a large specific surface in comparison with the powedered poly(ethylene terephthalate) prepared by mechanical milling. The specific surface value is influenced by the cooling rate of the initial homogeneous melt of poly(ethylene terephthalate)-6-caprolactam, by the concentration of poly(ethylene terephthalate) in this melt and by its molecular weight, by the water temperature at the extraction of 6-caprolactam from the tough mixed melt, by the drying temperature of the powdered poly(ethylene terephthalate), and by the content of residual 6-caprolactam in the powdered product. In the examined area, the specific surface value of the powdered poly(ethylene terephthalate) prepared by reprecipitation from the melt of 6-caprolactam ranged from 10 to 110 m²·g^?1.     

Correlation of solubility data of azo disperse dyes with the dye uptake of poly(ethylene terephthalate) fibres in supercritical carbon dioxide

Solubility data of disperse azo dyes in supercritical carbon dioxide are presented for dyeings of poly(ethylene terephthalate) fibres with CI Disperse Red 167:1, carried out at 200–300 bar and 80–120 °C, with varying amounts of adulterants. The same dyeings were also carried out in water for comparison. Scanning electron micrographs were taken of the dyes which show a growth of dye crystals during treatment in supercritical carbon dioxide. The paper reports that at 120 °C, melting of the pure dye CI Disperse Red 167:1 is observed. The presence of adulterants in the dye formulations help prevent agglomeration by acting as spacers between the dye molecules. Dyeings of PETP carried out under conditions of the highest solubility of the dye in supercritical carbon dioxide do not necessarily result in a very high dye uptake. This was shown by pressure- and temperature-dependent dyeing experiments of PETP in supercritical carbon dioxide.     

Studies in disperse dye transfer mechanism in polyester–viscose union at elevated temperatures

The thermofixation process of dyeing polyethylene terephthalate–viscose union fabric with disperse dyes has been experimentally studied with a view to understanding the phenomena of dyeing polyester blends. It is shown how the distribution of a disperse dyestuff changes on the terylene and viscose portions of a union during different stages of dyeing by the thermofixation process. Equilibrium adsorption isotherm and rate curves of adsorption of disperse dyes on the polyester portion of the union have been determined. The nature of staining of the viscose portion of the union with different disperse dyes has been investigated. From the presented typical data it is possible to deduce fairly simple semiempirical rules regarding the phenomena of the thermofixation process of dyeing polyester–viscose union. It is pointed out that it is not possible to derive an exact thermodynamic theory to explain the data and describe the molecular mechanisms in such systems.     

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     

Structure–properties relations of the drawn poly(ethylene terephthalate) filament sewing thread

This article presents research into draw ratio influence on the structure–properties relationship of drawn PET filament threads. Structural modification influence due to the drawing conditions, i.e., the birefringence and filament crystallinity, on the mechanical properties was investigated, as well as the shrinkage and dynamic mechanical properties of the drawn threads. Increasing draw ratio causes a linear increase in the birefringence, degree of crystallinity, filament shrinkage, and a decrease in the loss modulus. In addition, loss tangent and glass transition temperature, determined at the loss modulus peak, were increased by drawing. The observed structural changes influence the thread's mechanical properties, i.e., the breaking tenacity, elasticity modulus, and tension at the yield point increase, while breaking extension decreases by a higher draw ratio. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of structural changes on dye diffusion in poly(ethylene terephthalate)

The diffusion of a disperse dye, 1-amino-4-hydroxyanthraquinone (C.I. Disperse Red 15) into poly(ethylene terephthalate) fibers has been studied as a function of heatsetting temperature and draw ratio. It was found that the dynamic loss modulus E″, measured under the dyeing conditions, was related to the dye diffusivity D. This indicates that the diffusion is controlled by the mobility of the polymer chain segments. Both the diffusivity and dye saturation values do not vary monotonically with heatsetting temperature but exhibit a minimum at a heat-setting temperature near 175°C. X-ray diffraction measurements were used to show that this behavior is attributable to crystallinity and crystal size changes resulting from heat-setting.