High birefringence of poly(trimethylene terephthalate) spherulite

Poly(trimethylene terephthalate) (PTT) spherulite shows interference color under polarized light microscope without a sensitive tint plate. The fact indicates that the retardation of PTT spherulite is high, while it was reported that the birefringence in PTT fiber is low. In this study, the reason why the high birefringence is observed in PTT spherulite was discussed. By small area X-ray diffraction measurement, it was confirmed that a-axis of unit cell of PTT crystal was parallel to the radial direction of the spherulite. Based on the result, we calculated the refractive indices of parallel to a-axis and the other orthogonal directions. It was clarified that the refractive index of a-axis is much lower than the others and the intrinsic birefringence for a-axis orientation is high. It is the reason why the PTT spherulite shows high and negative birefringence.     

Nanofibrous mats of poly(trimethylene terephthalate) via electrospinning

Nanofibrous mats were prepared by electrospinning of poly(trimethylene terephthalate) (PTT) with diameter ranging from 200 to 600 nm. Morphology of electrospun nanofiber obtained by changing processing parameters such as solution concentration and their deposition time, was investigated with scanning electron microscope (SEM). Especially, periodic feature of surface roughness, such as diamond-shaped structure, was exhibited as the deposition time increased. In this work, it was shown that this phenomenon might result from polymer chain mobility, which was induced by solvent properties, and point bonding structure. In addition, schematic diagram was introduced to identify the formation of diamond-shape structure in PTT electrospun nanofibrous mats.     

Crystallization, and morphology of poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) segmented block copolymers

A new type of poly(ether-ester) based on poly(trimethylene terephthalate) as rigid segments and poly(ethylene oxide terephthalate) as soft segments was synthesized and its crystallization behavior and morphology were investigated. Differential Scanning Calorimetry revealed that the copolymer containing 57 wt% soft segments presented a low glass transition temperature (−46.4 °C) and a high melting temperature (201.8 °C), suggesting that it had the typical characteristic of thermoplastic elastomer. With increasing soft segment content from 35 to 57 wt%, the crystallization morphology transformed from banded spherulites to compact seaweed morphology at a certain film thickness, which was due to the change of surface tension and diffusivity caused by increasing the soft segment content. Moreover, with the decrease of film thickness from 15 to 2 μm, the crystallization morphology of the copolymer (57 wt% soft segment) changed from wheatear-like, compact seaweed to dendritic. Scanning Electron Microscopy revealed that some flower-like crystals presenting in the bulk, which had been surprisingly found in the poly(ether-ester) segmented block copolymers for the first time. Possible mechanism was discussed in the text.     

Crystallization kinetics and morphology of poly(trimethylene terephthalate)

In this work, the isothermal crystallization kinetics of polytrimethylene terephthalate (PTT) was first investigated from two temperature limits of melt and glass states. For the isothermal melt crystallization, the values of Avrami exponent varied between 2 and 3 with changing crystallization temperature, indicating the mixed growth and nucleation mechanisms. Meanwhile, the cold crystallization with an Avrami exponent of 5 indicated a character of three-dimensional solid sheaf growth with athermal nucleation. Through the analysis of secondary nucleation theory, the classical regime I→II and regime II→III transitions occurred at the temperatures of 488 and 468 K, respectively. The average work of chain folding for nucleation was ca. 6.5 kcal mol⁻¹, and the maximum crystallization rate was found to be located at ca. 415 K. The crystallite morphologies of PTT from melt and cold crystallization exhibited typical negative spherulite and sheaf-like crystallite, respectively. Moreover, the regime I→II→III transition was accompanied by a morphological transition from axialite-like or elliptical-shaped structure to banded spherulite and then non-banded spherulite, indicating that the formation of banded spherulite is very sensitive to regime behavior of nucleation.     

Effects of crystallization behavior on morphological change in poly(trimethylene terephthalate) spherulites

In poly(trimethylene terephthalate) (PTT) spherulites during isothermal crystallization, the morphological changed from an axialite/or elliptical banded spherulite to banded spherulite and then non-banded spherulite with temperature decreasing were studied by following the lamellar growth behaviors. We report lamellar growth mechanism on varied crystallization temperature, which explicitly probes the link between microscopic structure and macroscopic morphology in the development of patterns. Fibrillation of the edge-on lamellae was observed on the surfaces of axialite and the convex bands of banded spherulite. Terrace-like lamellae were observed on the surface of the non-banded spherulite and the concave bands of banded-spherulite. In thin film crystallization, PTT banded spherulite exhibits a texture of alternate edge-on and flat-on lamellae, wavy-like surface and rhythmic growth. The deceleration of growth rate takes place in convex bands with a growth habit of fibrillation of the edge-on lamellae for emerging ridge surface. On the other hand, the acceleration of growth rate appears in concave bands with a growth habit of terrace-like lamellae for emerging valley surface. The alternating growth mechanism of the lamellae was considered to be related with the formation of spatiotemporal self-organization patterns far from equilibrium. In order to explain the rhythmic growth and periodic growth of the lamellae, we may conjecture that the emergence of PTT banded spherulite in thin film crystallization is associated with an oscillatory dynamics of the spherulite growth front driven by latent heat diffusion. We present some tentative ideas on the possibility of band-to-nonband (BNB) morphological transition, which might be analogous with the second order transition in non-equilibrium phase transition.     

Thermal decomposition kinetics of thermotropic poly(oxybenzoate‐co‐trimethylene terephthalate)

A new kind of thermotropic liquid crystalline, poly(oxybenzoate‐co‐trimethylene terephthalate), was prepared from p‐hydroxybenzoic acid (B) and poly(trimethylene terephthalate) (PTT or T) by melting polycondensation. The monomer ratio of B to T is 60:40. The dynamic thermogravimetric kinetics of the copolymer B/T (60:40) and PTT in nitrogen were analyzed by four single heating rate techniques and two multiple heating rate techniques. The effects of the heating rate and the calculating technique on the thermostable and degradation kinetic parameters of the B/T copolymer and PTT are systematically discussed. The four single heating rate techniques used in this work include Friedman, Freeman‐Carroll, Chang, and the second Kissinger techniques, whereas the two multiple heating rate techniques are the first Kissinger and Flynn‐Wall techniques. Additionally, the isothermal thermogravimetric kinetics of B/T (60:40) in nitrogen were investigated by the Flynn technique. The activation energy, the order, and the frequency factor of the degradation reaction for B/T (60:40) copolymer are determined to be 185 kJ/mol, 1.8, and 7.14 × 10¹³ min⁻¹, respectively. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2025–2036, 2000     

Dynamic mechanical and dielectric relaxation characteristics of poly(trimethylene terephthalate)

The dynamic mechanical and dielectric relaxation properties of a commercial poly(trimethylene terephthalate) [PTT] have been investigated for both quenched and isothermally melt-crystallized specimen films. The relaxation characteristics of PTT were consistent with those of other low-crystallinity semiflexible polymers, e.g. PET and PEEK. While the sub-glass relaxation was largely unperturbed by the presence of the crystalline phase, both calorimetric and broadband dielectric measurements across the glass transition indicated the existence of a sizeable rigid amorphous phase (RAP) fraction in melt-crystallized PTT owing to the constraining influence of the crystal surfaces over the crystal-amorphous interphase region. A strong increase in measured dielectric relaxation intensity (Δ?) with temperature above T_g indicated the progressive mobilization of the RAP material, as well as an overall loss of correlation amongst the responding dipoles.     

Dielectric relaxation of poly (trimethylene terephthalate) in a broad range of crystallinity

Here we present dielectric relaxation experiments carried out in semicrystalline poly (trimethylene terephthalate) (PTT) samples covering a broad range of crystallinity values. Special attention has been devoted to characterize the two extremes of low and high crystallinity. In particular a high temperature relaxation in the dielectric spectra of highly crystalline PTT, attributed to a Maxwell–Wagner–Sillars process, has been revealed. Moreover, the existence of ordering phenomena during the induction period prior to crystallization has been characterized by dielectric spectroscopy.     

Structure and property studies of poly(trimethylene terephthalate) high-speed melt spun fibers

Poly(trimethylene terephthalate) has been melt spun at various take-up velocities from 0.5 to 8 km/min to prepare fiber samples. The effect of take-up velocity on the structure and properties of as-spun fibers has been characterized through measurements of birefringence, density, wide-angle X-ray scattering, DSC melting behavior, tensile properties and boiling water shrinkage (BWS). The birefringence exhibits a maximum at take-up velocities between 3 and 4 km/min. The fiber samples spun at the lower take-up speeds have essentially amorphous structures, while the filaments prepared at a velocity range higher than 4 km/min all possess an obvious crystalline structure. With increasing take-up speed, a steady improvement in tensile strength, elongation to break, and BWS is found, whereas the initial modulus remains almost constant within the measurement error, over the entire take-up speed range between 0.5 and 8 km/min.     

Isothermal gravimetric analysis of poly(trimethylene terephthalate)

Poly(trimethylene terephthalate) was investigated by isothermal thermogravimetry in nitrogen at six temperatures, including 304, 309, 314, 319, 324, and 336°C. The isothermal data have been analyzed using both a peak maximum technique and an iso‐conversional procedure. Both techniques gave apparent activation energies of 201 and 192 kJ mol^?1, respectively, for the isothermal degradation of poly(trimethylene terephthalate) in nitrogen. The decomposition reaction order is calculated to be 1.0. The natural logarithms of the frequency factor based on the peak maximum and the iso‐conversional techniques are 36 and 34 min^?1, respectively, for poly(trimethylene terephthalate) decomposed isothermally in nitrogen. These isothermal kinetic parameters are in good agreement with those derived by the Kissinger technique on the basis of the dynamic thermogravimetric data reported elsewhere (209 kJ mol^?1, 1.0 and 37 min^?1). The isothermal decomposition of poly(trimethylene terephthalate) in nitrogen undergoes two processes, a relative fast degradation process in the initial period and a subsequent one with a slower weight‐loss rate. The former process may be due to the removal of ester groups, trimethylene groups, and aromatic hydrogen atoms from the chain of poly(trimethylene terethphalate). The latter one may be ascribed to the further pyrolysis of the carbonaceous char. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1600–1608, 2002; DOI 10.1002/app.10476     

Alkaline depolymerization of poly(trimethylene terephthalate)

The purpose of this study was to investigate the effects of reaction media, composition, and temperature on the rate of the alkaline depolymerization of poly(trimethylene terephthalate) (PTT). The alkaline depolymerization of PTT was carried out at 160–190°C in ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), ethylene glycol monobutyl ether (EGMBE), diethylene glycol monoethyl ether (DEGMEE), and a mixture of these solvents. During the reaction, PTT was quantitatively converted to disodium terephthalate and 1,3-propanediol. The alkaline depolymerization reaction rate constants were calculated based on the concentration of sodium carboxylate, which was equivalent to the molar amount of sodium hydroxide. The depolymerization rate of PTT was increased by increasing the reaction temperature and by adding ethereal solvents. Moreover, the depolymerization rate was significantly accelerated in the order of EG < DEG < TEG < EGMBE < DEGMEE. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 99–107, 2001     

Crystallization temperature dependence of interference color and morphology in poly(trimethylene terephthalate) spherulite

The relationship between retardation and morphology in highly birefringent poly(trimethylene terephthalate) spherulites was studied from the viewpoint of crystallization temperature dependence. Both the retardation and the morphology relate with the degree of orientation of the molecular chains. Therefore, the degree of orientation of the crystal lamellae was estimated by image processing of transmission electron microscope (TEM) images of the spherulite. It was found that the degree of orientation changed remarkably between the non-banded and the banded morphology and the temperature dependence of the degree of orientation correlated with that of the retardation. Based on the image-processed TEM images, it was recognized that the crystal lamellae formed bundles in the banded spherulite, while few bundled lamellae were observed in the non-banded ones. It is suggested that the formation of bundled lamellae played the significant role for both the magnitude of retardation and determination of the morphology; i.e. whether to form banded spherulites or non-banded ones.     

Crystallization and melting behaviors of poly(trimethylene terephthalate)

The crystallization and melting behaviors of poly(trimethylene terephthalate) (PTT) have been studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and solid-state NMR. At certain crystallization temperatures (T_c) for a given time, the isothermally crystallized PTT exhibits two melting endotherms, which is similar to that of PET and PBT. At higher crystallization temperature (T_c = 210 °C), the low-temperature endotherm is related to the melting of the original crystals, while the high-temperature endotherm is associated with the melting of crystals recrystallized during the heating. The peak temperatures of these double-melting endotherms depend on crystallization temperature, crystallization time, and cooling rate from the melt as well as the subsequent heating rate. At a low cooling rate (0.2 °C/min) or a high heating rate (40 °C/min), these two endotherms tend to coalesce into a single endotherm, which is considered as complete melting without reorganization. WAXD results confirm that only one crystal structure exists in the PTT sample regardless of the crystallization conditions even with the appearance of double melting endotherms. The results of NMR reveal that the annealing treatment increases proton spin lattice relaxation time in the rotation frame, T_1ρ ^H, of the PTT. This phenomenon suggests that the mobility of the PTT molecules decreases after the annealing process. The equilibrium melting temperature (T _m ^o ) determined by the Hoffman-Weeks plot is 248 °C.     

聚对苯二甲酸丙二醇酯的热降解性能

采用了旋转流变仪、凝胶色谱等仪器对聚对苯二甲酸丙二醇酯(PTT)的热降解性能进行了研究。研究表明:随着时间的延长,PTT熔体的相对分子质量和熔体黏度明显下降,而相对分子质量分布没有明显变化;随着温度的升高,PTT熔体的降解速度明显增大;在不同剪切速率下,两种国外PTT熔体的热降解速率基本相同;PTT相对分子质量越高,越易发生热降解。     

Effects of reactive compatibilizer on the core-shell structured modifiers toughening of poly(trimethylene terephthalate)

Poly(trimethylene terephthalate)/polybutadiene grafted polymetyl methacrylate (PB-g-PMMA, MB) blends were prepared by melt processing with varying weight ratios (0-5 wt%) of diglycidyl ether of bisphenol-A (DGEBA) epoxy resin as a reactive compatibilizer. DMA result showed PTT was partially miscible with MB particles in the presence of the compatibilizer. Fourier transform infrared (FTIR) and rheological measurements further identified the reactions between PTT and DGEBA epoxy resin. Scanning electron microscopy (SEM) displayed that the core-shell structured modifiers exhibit a smaller dispersed domain size with the addition of DGEBA epoxy resin. Mechanical tests showed the impact and tensile properties of PTT blends are improved by the introduction of DGEBA epoxy resin to the blends. SEM and TEM results showed shear yielding of PTT matrix and cavitation of rubber particles were the major toughening mechanisms.     

Thermal stability of poly(ethylene‐co‐trimethylene terephthalate)s

The thermal stability of poly(ethylene‐co‐trimethylene terephthalate) was first studied by thermogravimetry under nitrogen atmosphere at different heating rates. The results showed that the thermal behavior of the copolyester had a strong dependence on the chemical composition. The average activation energy from Ozawa technique increases with the concentration of EG units in the polyester, and a greater TG concentration in the copolyesters would decrease the onset degradation temperature. These phenomena may be attributed to the presence of one more methylene of TG unit than of EG in the copolymer. It is also noted that the yield of solid residue increases with the concentration of EG units in the polymer chain at any heating rate, which may be associated with the content of aromatic ring in the polymer chain. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3330–3335, 2006     

Effect of uniaxial drawing on surface chain structure and surface tension of poly(trimethylene terephthalate) film

Changes in the surface chain structure and the critical surface tension of poly(trimethylene terephthalate) (PTT) film under uniaxial drawing were examined by polarized attenuated total reflection infrared (ATR-IR) spectroscopy and contact angle measurement. It was observed from the stress-draw ratio curve and density measurement that the strain-induced crystallization occurs at the draw ratio of 2.5. From the ATR-IR spectra, it was also realized that the surface chain structure changes with the draw ratio, showing a remarkable increase in the surface crystallinity at the draw ratio between two and three. The critical surface tension of uniaxially drawn films increases with the draw ratio due to an increase in the surface crystallinity developed by the strain-induced crystallization. It is concluded that the surface properties of PTT film such as the chain structure at the surface and the critical surface tension are very closely related to the condition of uniaxial drawing.     

Effects of reprocessing on the structure and mechanical properties of poly(trimethylene terephthalate)

The effects of reprocessing by extrusion for up to four cycles on the structure and mechanical properties of poly(trimethylene terephthalate) (PTT) were studied. Reprocessing did not change the chemical structure of the polymer but led to both yellowing and molecular weight reduction. Young's modulus and the yield stress of PTT remained constant or decreased with successive extrusion cycles, probably because of the observed slight specific volume increase. The continuous reduction in the break properties due to reprocessing was smaller than that found in similar polyesters and was attributed to the molecular weight reduction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2775–2780, 2002     

Effect of aging on the mechanical properties of cold-crystallized poly(trimethylene terephthalate)

The changes in the mechanical and thermal properties of cold-crystallized poly(trimethylene terephthalate) during aging at 60 and 80 °C were investigated. A significant increase in the tensile modulus and stress at yield and a decrease in strain at yield were observed for both aging temperatures. Differential scanning calorimetry (DSC) scans of the aged sample showed an endothermic annealing peak 10-20 °C above the previous aging temperature, the maximum temperature and enthalpic content of these peaks increased with aging time. Dynamic mechanical measurements indicated a relaxation process starting at about 20 °C above the aging temperature and correlate with the annealing peak detected by DSC. Density measurements and wide-angle X-ray scattering investigation revealed that neither the crystallinity increased significantly nor did the crystal structure changed. These results were explained by the existence of a third phase besides the crystalline and the ‘classical amorphous’ which involves oriented and constrained ‘non-crystalline’ polymer chain sequences close to the crystalline lamellae.     

Depolymerization of poly(trimethylene terephthalate) in supercritical methanol

The depolymerization of poly(trimethylene terephthalate) (PTT) in supercritical methanol was carried out with a batch‐type autoclave reactor at temperatures ranging from 280 to 340°C, at pressures ranging from 2.0 to 14.0 MPa, and for reaction time of up to 60 min. PTT quantitatively decomposed into dimethyl terephthalate (DMT) and 1,3‐propaniol (PDO) under the designed conditions. The yields of DMT and PDO greatly increased as the temperature rose. The yields of the monomers markedly increased as the pressure increased to 10.0 MPa, and they leveled off at higher pressures. The final yield of DMT at 320°C and 10.0 MPa reached 98.2%, which was much closer to the extent of the complete reaction. A kinetic model was used to describe the depolymerization reaction, and it fit the experimental data well. The dependence of the forward rate constant on the reaction temperature was correlated with an Arrhenius plot, which gave an activation energy of 56.8 kJ/mol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2363–2368, 2004