Synthesis and characterization of poly[(butylene succinate)‐co‐(butylene terephthalate)]‐b‐poly(tetramethylene glycol) segmented block copolymer

Polyester‐polyether segmented block copolymers of poly[(butylene succinate)‐co‐poly(butylene terephthalate)] (PBS–PBT) and poly(tetramethylene glycol) (PTMG) (M_n = 2000) with various compositions were synthesized. PBT content in the PBS was adjusted to ca. 5 mol %. Their thermal and mechanical properties were investigated. In the case of copolymer, the melting point of the PBS–PBT control was 107.8°C, and the melting point of the copolymer containing 70 wt % of PTMG was 70.1°C. Crystallinity of soft segment was 5 ∼ 17%, and that of hard segment was 42 ∼ 59%. The breaking stress of the PBS–PTMG control was 47 MPa but it decreased with increasing PTMG content. In the case of copolymer containing 70 wt % of PTMG, breaking stress was 36 MPa. Contrary to the decreasing breaking stress, breaking strain increased from 300% for PBS–PBT control to 900% for a copolymer containing 70 wt % of PTMG. The shape recovery ratios of the copolymer containing 70 wt % PTMG were almost twice of those of copolymers containing 40 wt % PTMG. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2067–2075, 2001     

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     

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.     

Mechanical properties in torsion for poly(butylene terephthalate) and a poly(ether ester) based on poly(ethylene glycol) and poly(butylene terephthalate)

The torsional behavior of poly(ether ester) (PEE) thermoplastic elastomer, based on poly(ethylene glycol) (PEG) and poly(butylene terephthalate) (PBT) was studied and compared with that of PBT itself. Two types of experiments were performed: (1) stress relaxation in torsion, and (2) measurement of intermittent couple-twist responses. It was shown that the relaxation of the torsional couple M could be represented as a sum of several exponential terms in the time, rather than as a simple exponential function. This sum might be called a Prony series on the analogy of the usual stress relaxation which occurs after stretching a sample to a certain deformation and holding it constant. The intermittent couple-twist experiments were carried out by analogy with similar experiments in elongation. For PEE the couple rises steadily with the twist, whereas for PBT it rises abruptly and remains constant within the experimental error for high twists. The residual twist, however, showed a similar trend for both PEE and PBT. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 495–502, 1998     

Preparation and thermal behavior of random poly(butylene terephthalate/azelate) copolyesters

Poly(butylene terephthalate), poly(butylene azelate), and poly(butylene terephthalate/butylene azelate) random copolymers of various compositions were synthesized in bulk using the well‐known two‐stage polycondensation procedure, and characterized in terms of chemical structure and molecular weight. The thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. As far as the thermal stability is concerned, it was found to be rather similar for all copolymers and homopolymers investigated. All the copolymers were found to be partially crystalline, and the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to pure homopolymers. Flory's equation was found to describe the T_m–composition data and permitted to calculate the melting temperatures (T^°_m ) and the heats of fusion (ΔH_u) of both the completely crystalline homopolymers. Owing to the high crystallization rate, the glass transition was observable only for the copolymers containing from 30 to 70 mol % of the terephthalate units; even though the samples cannot be frozen in a completely amorphous state, the data obtained confirmed that the introduction of the aromatic units gave rise to an increase of T_g, due to a chain stiffening. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2694–2702, 1999     

Rheology modification of PVC plastisols with poly(butylene terephthalate)-b-poly(tetramethylene glycol)

A few percent of poly(butylene)-b-poly(tetramethylene glycol) was able to turn a liquid plasticizer into a gel, and thus imparted yield stresses to the fluid. When the plasticizer contained as little as 2.5 wt % of the block copolymer, sag free plastisols were obtained. A reduction in tensile strength was found for the modified plastisols, while the elongation was not affected. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 749–753, 1997     

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 behaviour of poly(butylene succinate) copolymers

Poly(butylene succinate‐co‐butylene 2‐methyl succinate) (PBSMS) random copolymers were synthesized with various comonomer compositions and their crystallization behaviour and morphology were investigated by differential scanning calorimeter, small angle X‐ray scattering and polarized optical microscopy. The equilibrium melting temperature obtained by the Hoffman–Weeks plot significantly decreased with increasing comonomer concentration containing methyl side‐groups. Spherulitic growth rates were strongly dependent on comonomer concentration and were analyzed using the Lauritzen–Hoffman kinetic theory. The surface free energy (σσ_e) dramatically decreased with comonomer contents. From analysis of the SAXS data, the dependence of the lamellar thickness on crystallization temperature decreased with increasing comonomer concentration. © 2002 Society of Chemical Industry     

Structure and mechanical properties of poly(sulfone of bisphenol A)/poly(butylene terephthalate) blends

Blends of poly(sulfone of bisphenol A) (PSU) with poly(butylene terephthalate) (PBT) were obtained by direct injection moulding across the composition range. The two components of the blends reacted slightly in the melt state, producing linear copolymers. The slight changes observed in the two glass transition temperatures indicate that the copolymers were present in the two amorphous phases of the blends. The observed reactions and the high viscosity of the matrix of the PSU‐rich compositions led to a very fine morphology which could not be attained in the PBT‐rich compositions due to the low viscosity of the matrix and the direct injection moulding procedure used. This procedure is fast and economically advantageous, but leads to poor mixing. The different morphologies influenced neither the modulus nor the yield stress, which tended to follow the rule of mixtures. However, the low fracture properties of the PBT‐rich compositions contrasted with the ductility behaviour, and even the impact strength of the PSU‐rich blends, which also tended to be proportional to the blend composition. Copyright © 2004 Society of Chemical Industry     

Crystallization behavior and morphology of double crystalline poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers

Double crystalline poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers (PTT/PEOT), with PTT content ranging from 16.5 to 65.5 wt%, were synthesized by melt copolycondensation. The morphological transformation of samples from microphase separation to macrophase separation was investigated by gel permeation chromatography and transmission electron microscopy. Differential scanning calorimetry and in situ wide‐angle X‐ray diffraction suggested that all copolycondensation samples displayed double crystalline behavior. The melt‐crystallization peak temperatures (T_{m, c} values) of PTT chains monotonously increased with increasing PTT content and were higher than that of homo‐PTT when the content of PTT was above 30.6 wt%. Interestingly, T_{m, c} values of PEOT chains were also increased with increasing PTT content. Polarized optical microscopy revealed that all copolycondensation samples studied could form ring‐banded spherulites and band spacing increased with increasing T_c values. In addition, band spacing decreased with increasing PTT content at a given T_c. Strangely, although PEOT was the main component in all copolycondensation samples, spherulitic morphology formed by the advance crystallization of PTT did not change after PEOT crystallization. Only a subtle change of quadrant tones was detected. © 2012 Society of Chemical Industry     

Critical inter-particle distance dependence and super-toughness in poly(butylene terephthalate)/grafted poly(ethylene-octene) copolymer blends by means of polyarylate addition

New super-tough poly(butylene terephthalate) (PBT) materials were obtained modifying with 10 wt% polyarylate (PAr) a PBT/maleic anhydride grafted poly(ethylene-octene) copolymer (mPEO) blend with mPEO contents from 0 to 30 wt%. PAr was fully miscible in the PBT phase. The presence of mPEO did not influence either the nature or the crystallinity of the PBT-PAr matrix. The decrease in interfacial tension and particle size upon grafting of PEO, indicated that compatibilization took place. The maximum toughness obtained was very high (impact strength more than twenty-fold that of the PBT-PAr matrix). Moreover, it was attained with only 7.5% PEO maleinized at 0.63%, and was accomplished by an increase in stiffness of the blends. The successful modification of the matrix consolidates this method as a new one to improve impact toughness. The critical inter-particle distance (τ_c) appears as the parameter that control super-toughness in these blends, and it is proposed to depend on adhesion measured by means of the interfacial tension.     

Microhardness under strain. III. Microhardness behavior during stress-induced polymorphic transition in blends of poly(butylene terephthalate) and its block copolymers

The microhardness (H) technique was recently applied to poly(butylene terephthalate) (PBT) and its multiblock copolymer of poly(ether ester) (PEE) type for examination of the stress-induced polymorphic transition. In the present study, these investigations are extended to blends of PBT and PEE. For this purpose, drawn and annealed with fixed ends at 170°C for 6 h in vacuum bristles of PBT–PEE, blends were characterized with respect to their microhardness at various stages of tensile deformation. H was measured under stress, with each step of deformation amounting 5%. The variation of H with strain (ε) shows 2 sharp stepwise decreasing values (by 40%). Each step is defined in a relatively narrow deformation (ε) range (2–5%) due to the stress-induced α → β polymorphic transitions arising in PBT crystallites. The first polymorphic transition (at ε = 2–3%) is assigned to the PBT crystallites of the homopolymer (homoPBT). The second transition (at ε = 25%) is associated to those crystals within the PEE copolymer. From the observation of two distinct transitions, separated by a deformation interval of ε = 20% it is concluded that (1) homoPBT and the PBT segments from PEE crystallize separately (no cocrystallization takes place), and (2) the 2 species of PBT crystallites are subject to the external mechanical loading, not in a simultaneous manner, but in a two-stage process. In the deformation range between the 2 transitions (ε = 2–3% and 25%), it is pointed out that conformational changes are induced through stretching, mainly in the amorphous regions. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2271–2276, 1998     

Chain extension of poly(butylene terephthalate) by reactive extrusion

The chain extension reaction in poly(butylene terephthalate) (PBT) melt was studied in detail. A high‐reactivity diepoxy, diglycidyl tetrahydrophthalate, was used as a chain extender that can react with the hydroxyl and carboxyl end groups of PBT at a very fast reaction rate and a relatively high temperature. A Haake mixer 600 was used to record the torque during the chain extension reaction. The data show that this chain extension reaction could be completed within 2 to 3 min at temperatures above 250°C, and the reaction time decreased very fast with an increase in the temperature. Shear rate also had some effects on the reaction rate. The effect of the diepoxy chain extender on the flowability, thermal stability, and mechanical properties of PBT were investigated. The melt flow index (MFI) of the chain‐extended PBT dramatically decreased as the diepoxy was added to PBT. In addition, the notched Izod impact strength and elongation‐at‐break of the chain‐extended PBT also increased. The chain‐extended PBT is more stable thermally. Compared with the conventional solid post‐polycondensation method, this approach is simpler and cheaper to obtain high‐molecular‐weight PBT resins. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1827–1834, 1999     

A constitutive law for poly(butylene terephthalate) nanofibers mats

A three‐dimensional structural constitutive equation is proposed to describe the mechanical properties of poly(butylene terephthalate) nanofibers mats. The model is formulated under the assumption that the mechanical response of the fibrous mat is determined by the individual fibers. The inelasticity, which has been observed when subjecting the fibrous mat to tensile tests, is assumed to be due to the gradual breakage of linear elastic fibers. The constitutive relation also takes the material anisotropy associated with the fibers' architecture into account. Uniaxial experimental data were used to assess the proposed model. The results demonstrate that the model is well suited to reproduce the typical tensile behavior of the fibrous mat. In agreement with the empirical observations, the model predicts that almost all the fibers fail when the poly(butylene terephthalate) fibrous mat sample breaks. Nevertheless, multiaxial stress–strain data and quantification of the fibers' orientation are required to completely validate the constitutive law. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5280–5283, 2006     

Sequence analysis of poly(ethylene terephthalate)/poly(butylene terephthalate) copolymer prepared by ester-interchange reactions

The molecular structure of the copolyester formed through the interchange reaction in poly(ethylene terephthalate)/poly(butylene terephthalate) blends was investigated with ¹³C-NMR spectroscopy. The molar fractions of heterolinkage triads in the copolyesters were lower than the values calculated by Bernoullian statistics; this indicates that the sequence of heterolinkages was far from a random distribution at the initial stage of the interchange reaction. However, the randomness increased and the number-average sequence length decreased with reaction time. The solubility of the blend decreased with increasing sequence length, resulting from the formation of block copolymers with long sequence lengths at the initial stage of the interchange reaction. The solubility of the copolyester formed by a dibutyltin dilaurate (DBTDL)-catalyzed reaction was higher than that of the copolyester formed by a titanium tetrabutoxide-catalyzed reaction; this is related to the fact that alcoholysis prevailed in the DBTDL-catalyzed reaction. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 159–168, 2001     

Hydrolytic stability of sulfonated poly(butylene terephthalate)

The hydrolysis of sulfonated poly(butylene terephthalate) copolymers was studied. Sulfonated poly(butylene terephthalate) copolymers, referred to as PBT-ionomers (PBTIs), were shown to hydrolyze faster than poly(butylene terephthalate) (PBT). An experiment designed to isolate the effect of the sulfonated isophthalate (SIP) moieties on hydrolysis rate showed that the SIP moieties were responsible for the faster hydrolysis. Experiments aimed at identifying the mechanism of influence of the SIP moieties on hydrolytic stability indicated that hydrolysis was enhanced by the presence of ionic multiplets which increase amorphous content, imbibe water, and perhaps exert a medium effect on the hydrolysis of esters associated with the ionic groups.     

Rheological and thermal properties of blends of modified poly(ethylene terephthalate) with p‐acetoxybenzoic acid and poly(butylene terephthalate)

Blending of thermotropic liquid crystalline polyesters (LCPs) with conventional polymers could result in materials that can be used as an alternative for short fiber‐reinforced thermoplastic composites, because of their low melt viscosity as well as their inherent high stiffness and strength, high use temperature, and excellent chemical resistance and low coefficient of expansion. In most of the blends was used LCP of 40 mol % of poly(ethylene terephthalate) (PET) and 60 mol % of p‐acetoxybenzoic acid (PABA). In this work, blends of several copolyesters having various PABA compositions from 10 to 70 mol % and poly(butylene terephthalate) (PBT) were prepared and their rheological and thermal properties were investigated. For convenience, the copolyesters were designated as PETA‐x, where x is the mol % of PABA. It was found that PET‐60 and PET‐70 copolyesters decreased the melt viscosity of PBT in the blends and those PBT/PETA‐60 and PBT/PETA‐70 blends showed different melt viscosity behaviors with the change in shear rate, while blends of PBT and PET‐x having less than 50 mol % of PABA exhibited totally different rheological behaviors. The blends of PBT with PETA‐50, PETA‐60, and PETA‐70 showed the morphology of multiple layers of fibers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1797–1806, 1999