Miscibility and melting behavior of poly(ethylene terephthalate)/poly(trimethylene terephthalate) blends

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 (T_g) and the measured T_g fit well with the predicted T_g value by the Fox equation and Gordon‐Taylor equation. In addition to that, a single composition‐dependent cold crystallization temperature (T_cc) value can be observed and it decreases nearly linearly with the low T_g 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 (T_mc) of the blends decreased with an increase of the minor component and the 50/50 sample showed the lowest T_mc value, which is also related to its miscible nature in the melting state. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Solid‐state polymerization of poly(trimethylene terephthalate)

The solid‐state polymerization (SSP) of poly(trimethylene terephthalate) (PTT) has been studied and compared with that of poly(ethylene terephthalate) (PET). Because PTT and PET share the same SSP mechanism, the modified second‐order kinetic model, which has successfully been used to describe the SSP behaviors of PET, also fits the SSP data of PTT prepolymers with intrinsic viscosities (IVs) ranging from 0.445 to 0.660 dL/g. According to this model, the overall SSP rate is ?dC/dt = 2k_a(C ? C_ai)², where C is the total end group concentration, t is the SSP time, k_a is the apparent reaction rate constant, and C_ai is the apparent inactive end group concentration. With this equation, the effects of all factors that influence the SSP rate are implicitly and conveniently incorporated into two parameters, k_a and C_ai. k_a increases, whereas C_ai decreases, with increasing SSP temperature, increasing prepolymer IV, and decreasing pellet size, just as for the SSP of PET. Therefore, the SSP rate increases with increasing prepolymer IV and increasing SSP temperature. The apparent activation energy is about 26 kcal/mol, and the average SSP rate about doubles with each 10°C increase in temperature within the temperature range of 200–225°C. The SSP rate increases by about 30% when the pellet size is decreased from 0.025 to 0.015 g/pellet. Compared with PET, PTT has a much lower sticking tendency and a much higher SSP rate (more than twice as high). Therefore, the SSP process for PTT can be made much simpler and more efficient than that for PET. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3188–3200, 2003     

Dynamic mechanical analysis of poly(trimethylene terephthalate)—A comparison with poly(ethylene terephthalate) and poly(ethylene naphthalate)

The fiber properties of PTT have been the subject of several reports, although very few reports describe the properties of molded specimens. In this work, the dynamic mechanical relaxation behavior of compression‐molded PTT films has been investigated. The added flexibility of the PTT was found to lower the temperature of the β‐ and α‐transitions relative to the PET and PEN. The results suggest that the β‐transition is at least two relaxations for PET and PTT due to the increase in the breadth of the relaxation. The results seem to support the hypothesized mechanism of others, in that the β‐transition involves the relaxation of the carbonyl entity and the aromatic C1–C4 ring flips for PTT and PET, and the relaxation of the carbonyl for PEN. The β*‐ and α‐transitions for all three polymers seem to be cooperative in nature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2791–2796, 2004     

Study of poly(trimethylene terephthalate) as an engineering thermoplastics material

Poly(trimethylene terephthalate) (PTT) was systematically studied as an engineering thermoplastics material. Crystallization rates, crystalline degrees, and mechanical properties of two commercial PTT polymers and one glass fiber–reinforced PTT compound were investigated and compared with those of poly(butylene terephthalate) (PBT). PTT raw polymers have crystallization temperature (T_c) values around 152°C, and their kneaded polymers show T_c values of about 177°C, about 15°C lower than the values of PBT polymers used in this study. From the exothermic heat values of DSC measurements, both PTT and PBT show the crystalline degree order greater than 30%. Injection‐molded PTT specimens and PBT specimens exhibit crystalline degrees from 18 to 32% and 23.8 to 30%, respectively. PTT polymers show higher tensile and flexural strengths, but lower impact strengths and elongations than those of PBT polymers. The low elongation behavior of PTT does not change with the intrinsic viscosity and the molder temperature. PTT‐GF30 promotes better mechanical properties than those of PBT‐GF30, close to those of PET‐GF30. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1657–1666, 2004     

Effective nucleating chemical agents for the crystallization of poly(trimethylene terephthalate)

This study focused on the crystallization promotion of poly(trimethylene terephthalate) (PTT), with an aim at engineering thermoplastics applications. The effects of organic sodium (Na) salts, including Na stearate, Na benzoate, disodium‐p‐phenolsulfonate (2Na‐p‐PS), disodium‐p‐hydroxybenzoate (2Na‐p‐HB), and the sodium ionomer of poly(ethylene‐co‐methacrylic acid) (Na‐EMAA), were investigated as nucleating chemical agents with differential scanning calorimetry and capillary viscometry. For comparison, the effect of fine talc powder was also examined. The chemical agents were generally more effective than fine talc powder. Na stearate and Na benzoate caused large‐scale decomposition of PTT. 2Na‐p‐PS was quite thermally stable and caused little decomposition. 2Na‐p‐HB was the most efficacious of the nucleating chemical agents and caused mild decomposition. Na‐EMAA was the most thermally stable and induced an increase in melt viscosity. A remarkable improvement in the crystallization rate of PTT was successfully attained at a minimum polymer decomposition cost by the introduction of a suitable amount of 2Na‐p‐PS, 2Na‐p‐HB, or Na‐EMAA or by the concurrent proper incorporation of both of the latter two agents. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 590–601, 2004     

PTT长丝瞬时拉伸回弹性能研究

在相同条件下对比研究了PET ,PTT和PBT 3种芳香族聚酯长丝的瞬时拉伸回弹性能 ,分析了测定条件对PTT长丝瞬时拉伸回弹性能的影响 ,并初步讨论了 3种芳香族聚酯长丝的瞬时拉伸回弹机理。结果表明 ,PTT长丝的瞬时拉伸回弹性能明显优于PBT长丝 ,更优于PET长丝 ,PTT长丝在低伸长率和高伸长率下均具有优异的瞬时拉伸回弹性能 ;测定PTT长丝瞬时拉伸回弹率时 ,建议采用 0 .5cN/tex的预张力 ,5 0 0mm/min的拉伸速率和 2 0 %的定伸长率等条件     

Structure and mechanical properties of poly(trimethylene terephthalate)/poly(hydroxy ether of bisphenol A) blends

Compatible poly(trimethylene terephthalate) (PTT)/poly(hydroxy ether of bisphenol A) (Phenoxy) blends were obtained by direct injection molding throughout the composition range. Two amorphous phases with minor amounts of the other component were found in the blends. Reactions occurred in PTT‐rich blends. By comparing the miscibility level of these blends with that of other blends based on polyalkylene terephthalates, it is proposed that a miscibility limit delimited by a 3/1 methylene–carbonyl ratio in the polyalkylene terephthalate exits in these blends. The synergism in the Young's modulus of the blends is discussed as a consequence of the changes in the crystallinity of PTT, the specific volume and the orientation produced by blending. Ductility is approximately proportional to blend composition, indicating compatibility, and is attributed to the combined effects of a small particle size and a good adhesion level, the latter being a consequence of the partially miscible nature of the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3246–3254, 2006     

Surface hydrolysis of filaments based on poly(trimethylene terephthalate) spun at high spinning speeds

The surface alkaline hydrolysis of fibers made from poly(trimethylene terephthalate) (PTT) was studied after extruding the polymer at high spinning speeds from 2000 to 6000 m/min and heat setting in the range of temperatures from 100 to 180°C. Fiber weight loss increased with an increasing heat‐setting temperature but it was also dependent on the spinning speed. Some of the partially hydrolyzed fibers had a well‐developed, hydrophilic surface, and pore size in the range of 0.69 to 1.20 μm. The optimum reaction and morphological conditions for increasing porosity in PTT fibers depends on spinning speed and heat‐setting temperature. A temperature of 180°C is the upper limit for heat‐setting PTT filaments but seems to be the most effective for making porous fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1724–1730, 2004     

Determination of intrinsic physical constants of poly(trimethylene terephthalate) from drawn filament

The intrinsic lateral sonic moduli of the crystalline and amorphous regions of poly(trimethylene terephthalate) (3GT) (about 4.1504 ± 0.8396 GPa and 1.6096 ± 0.0368 GPa, respectively) were obtained from sonic moduli and crystallinities of unoriented 3GT filaments annealed under different conditions. Using the obtained intrinsic lateral sonic moduli of the crystalline and amorphous regions, the degree of orientation of the amorphous region of uniaxially drawn 3GT filaments could also be obtained from the crystallinity, sonic modulus, and the degree of crystalline orientation estimated from X‐ray azimuthal scan data. Thus, the intrinsic birefringences of the perfectly oriented crystalline and amorphous regions of the 3GT fibre (about 0.2057 ± 0.0160 and 0.2175 ± 0.0923, respectively) could be obtained from the appropriate combinations of birefringence, crystallinity, and the degree of orientation of the crystalline and amorphous regions. © 2003 Society of Chemical Industry     

Crystallization kinetics and melting behavior of poly[(trimethylene terephthalate)‐co‐(29 mol % ethylene terephthalate)] copolyester

The copolyester was characterized as having 71 mol % trimethylene terephthalate units and 29 mol % ethylene terephthalate units in a random sequence according to the NMR spectra. Differential scanning calorimeter (DSC) was used to investigate the isothermal crystallization kinetics in the temperature range (T_c) from 130 to 170°C. The melting behavior after isothermal crystallization was studied using DSC and temperature‐modulated DSC by varying the T_c, the crystallization time, and the heating rate. The DSC thermograms and wide‐angle X‐ray diffraction patterns reveal that the complex melting behavior involves melting‐recrystallization‐remelting and different lamellar crystals. As the T_c increases, the contribution of recrystallization gradually falls and finally disappears. A Hoffman‐Weeks linear plot yields an equilibrium melting temperature of 198.7°C. The kinetic analysis of the growth rates of spherulites and the change in the morphology from regular to banded spherulites indicate that a regime II→III transition occurs at 148°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Melting behavior of poly(trimethylene terephthalate)

In this study, the melting behavior of isothermally crystallized polytri‐ methylene terephthalate (PTT) was investigated. Multiple melting behaviors in DSC heating trace were found because two populations of lamellar stacks were formed during primary crystallization and the recrystallization at heating process, respectively. This fact could be also confirmed from the result of optical microscopy observation. The Hoffman–Weeks equation was applied to obtain equilibrium melting temperature (T). The T value of PTT is about 525 K, which is 10 K higher than that reported. Combining the enthalpy of fusion from the DSC result and the degree of crystallinity from WAXD result, the value of the equilibrium‐melting enthalpy ΔH was deduced to be approximately 28.8 kJ mol^?1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2426–2433, 2002     

Thermal stability of poly(trimethylene terephthalate)

The first-order thermal degradation rates of poly(trimethylene terephthalate) [PTT] at 240-280 °C under non-oxidative conditions have been determined from the increase in allyl endgroups (¹H NMR) which closely match the rates determined from the decrease in molecular weight (intrinsic viscosity). Consequently, the predominant thermal degradation mechanism of PTT is consistent with concerted, electrocyclic oxo retro-ene chain cleavage under conditions pertinent to viable polymerization processes and efficient downstream extrusion and spinning into fiber. Although catalysts, additives and other reaction variables can influence the thermo-oxidative stability of polyesters including PTT, these factors have been found to have little or no effect on PTT thermal degradation rates under non-oxidative environments. The thermal stability of poly(butylene terephthalate) [PBT] has also been determined from butenyl endgroups (NMR) and molecular weight (IV). The activation energies (E_a) for both PTT and PBT thermal chain cleavage are similar to the reported E_as for poly(ethylene terephthalate) [PET] degradation, which is further supported by semi-empirical molecular orbital calculations on model compounds. However, both PTT and PBT undergo molecular weight decrease faster than PET. The apparent slower chain cleavage of PET is attributed to the contribution of productive chain propagation reactions due to unstable vinyl endgroups which alters the equilibrium stoichiometry compared to the relatively stable endgroups of PTT and PBT.     

Crystallization kinetics of poly(trimethylene terephthalate)

The bulk isothermal crystallization kinetics of poly(trimethylene terephthalate) (PTT) was studied using a differential scanning calorimeter. Avrami's theory was used to analyze the data. Based on crystallinity growth rate, Avrami rate constant, K, and crystallization half‐time, PTT's crystallization rate is between those of poly(butylene terephthalate) (PBT) and poly(ethylene terephthalate) (PET) when compared at the same degree of undercooling. PBT has the highest crystallization rate with K in the order of 10^?2 to 10^?1 min^?n. It is about an order of magnitude faster than PTT at 10^?3 to 10^?2 min^?n, which in turn is an order of magnitude faster than PET with K of 10^?4 to 10^?2 min^?n. Contrary to previous reports (PTT was not included in the study) that aromatic polyesters with odd numbers of methylene units were more difficult to crystallize than the even‐numbered polyesters, PTT did not fit in the prediction and did not follow the odd‐even effect.     

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     

The structure of poly(trimethylene terephthalate)

The determination of the crystalline structure of oriented fibres of poly(trimethylene terephthalate) is described. The unit cell is triclinic with the following parameters: $\text{a = 4.6}\text{A}\text{?}$, $\text{b = 6.2}\text{A}\text{?}$, $\text{c = 18.3}\text{A}\text{?}$, α = 98°, β = 90°, γ = 112°. Each cell contains two monomers of one polymer chain. Both methylene bonds are in the gauche conformation. The chain conformation and the packing of chains within the unit cell are discussed in detail and compared with other chemically similar materials, both monomeric and polymeric.     

Reactive blending of aromatic polyesters: Thermal and X‐ray analysis of melt‐blended poly(ethylene terephthalate)/poly(trimethylene terephthalate)

We investigated the reactive melt blending of poly(ethylene terephthalate) (PET) and poly(trimethylene terephthalate) (PTT) in terms of the thermal properties and structural features of the resultant materials. Our main objectives were (1) to investigate the effects of the processing conditions on the nonisothermal melt crystallization and subsequent melting behavior of the blends and (2) to assess the effects of the blending time on the structural characteristics of the transreaction products with a fixed composition. The melting parameters (e.g., the melting temperature, melting enthalpy, and crystallization temperature) decreased with the mixing time; the crystallization behavior was strongly affected by the composition and blending time. Moreover, a significant role was played by the final temperature of the heating treatment; this meant that interchange reactions occurred during blending and continued during thermal analysis. The wide‐angle X‐ray diffraction patterns obtained under moderate blending conditions showed the presence of crystalline peaks of PET and PTT; however, the profiles became flatter after blending. This effect was more and more evident as the mixing time increased. Transesterification reactions between the polyesters due to longer blending times with an intermediate composition led to a new copolymer material characterized by its own diffraction profile and a reduced melting temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Cracking in poly(trimethylene terephthalate) spherulites

The crack behavior of poly(trimethylene terephthalate) spherulites was studied mainly by polarizing optical microscopy, along with scanning electron microscopy (SEM) and atomic force microscopy (AFM). In addition to the effects of temperature and constraining substrate, another important factor, film thickness, on the formation of crack was first put forward and investigated. The emergence of the first crack occurred at 120°C during cooling after crystallization at 190°C for the sample with a thickness of 31.0 μm. For the spherulites growing between glass sheets, it was interesting that the sample with a thickness of 26.0 μm exhibited the largest number of cracks measured per 200 μm of radius, whereas samples thicker than 100 μm or thinner than 1 μm did not induce the formation of crack. Also, spherulites growing between two polyimide and two Teflon sheets showed no crack. Glass sheets lubricated with silicon oil restrained the number of cracks but did not eliminate cracks. SEM revealed that the cracking was about 900 nm in width. In addition, the AFM results suggest that the cracks had a depth of at least 150 nm. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Efficient method for recycling poly(ethylene terephthalate) to poly(butylene terephthalate) using transesterification reaction

A method of recycling postconsumer poly(ethylene terephthalate (PET) using transesterification was studied. Shredded flakes of postconsumer PET waste were transesterified with higher diols, such as 1,4‐butanediol, 1,4‐cyclohexane dimethanol, and 1,6‐hexanediol, to yield copolyesters in the presence of Ti(iPrO)₄ and Sb₂O₃ as catalysts. The extent of the formation of undesirable tetrahydrofuran side products was dependent on the molar ratio of PET to1,4‐butanediol and the time of reflux during transesterification. Quantitative insertion of the butylene moiety into PET could be achieved under appropriate reaction conditions. The mechanical properties of PBT obtained by a transesterification reaction of PET with 1,4‐butanediol were comparable to those of virgin PBT (obtained by direct reaction of dimethyl terephathalate with 1,4‐butanediol). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3720–3729, 2004     

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     

Nanomechanical properties of poly(trimethylene malonate) and poly(trimethylene itaconate) during hydrolytic degradation

The aim of this work was to evaluate surface mechanical properties of two bioplastics, poly(trimethylene malonate) (PTM) and poly(trimethylene itaconate) (PTI), during hydrolytic degradation. Renewable resource‐based PTM and PTI were synthesized from 1,3‐propanediol (PDO), malonic acid (MA), and itaconic acid (IA) via melt polycondensation. The hydrolytic degradation was performed in deionized (DI) water (pH 5.4) at room temperature. Morphology and surface mechanical properties at the nanoscale were monitored by atomic force microscopy (AFM) using a quantitative nanomechanical property mapping mode as a function of degradation time. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to show shifted phase transitions depending on the degradation. DSC studies showed hydrolytic degradation induced crystallinity for PTI. After degradation for one week, the degree of crystallinity had significantly increased, and the elastic modulus of PTI had decreased by 58%. PTM was found to be hygroscopic. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41069.