Models for the formation of poly(butylene terephthalate): effect of water on the kinetics of the titanium tetrabutylate-catalysed reactions: 3

In an effort to investigate the mechanism of catalysis of titanium tetrabutoxide on the polycondensation of poly(butylene terephthalate), alcoholysis and hydrolysis reactions were studied with the aid of model molecules. The retarding effect of water has also been taken into account. Appropriate kinetic equations are derived and discussed and the results compared with experimental data obtained at different molar ratios of reactants.     

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.     

Toughening of poly(butylene terephthalate) by AES terpolymer

AES, a terpolymer of acrylonitrile-EPDM(ethylene/propylene/diene elastomer)-styrene, was blended in poly(butylene terephthalate) (PBT). Uniaxial tensile tests were carried out at various strain rates on blends containing 0-50 wt% of AES in order to study the yielding behavior of PBT in these blends by the Eyring equation. It was found that stress concentration factor (γ) increases sharply when a small content of AES is incorporated in the PBT matrix, but further incorporation seems to have small effect and γ levels out, a behavior that can be explained by the blend morphology and AES mechanical characteristics. The effect of AES content on the notched Izod impact strength of PBT blends was also examined in depth. It was found that a supertough blend can be achieved with at least 30 wt% of AES in PBT in appropriate molding temperature. Macroscopic and microscopic observations indicate that dilatational process play an important role on the toughening mechanism in PBT/AES blends at notched Izod impact tests.     

Synthesis and thermal characterization of poly(butylene terephthalate-co-thiodiethylene terephthalate) copolyesters

Poly(butylene terephthalate-co-thiodiethylene terephthalate) copolymers of various compositions were synthesized and characterized in terms of chemical structure and molecular weight. The thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. All the polymers under investigation show a good thermal stability. At room temperature they appear as semicrystalline materials: the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to homopolymers. A pure crystalline phase has been evidenced at high content of butylene terephthalate or thiodiethylene terephthalate units and Baur's equation was found to describe well the T_m-composition data. Amorphous samples (containing 50-100 mol% of thiodiethylene terephthalate units) showed a monotonic decrease of T_g as the content of sulfur-containing units is increased, due to the presence of flexible C-S-C bonds in the polymeric chain. Finally, the Fox equation described well the T_g-composition data.     

Toughening of poly(butylene terephthalate) with epoxy-functionalized acrylonitrile-butadiene-styrene

Glycidyl methacrylate (GMA) functionalized acrylonitrile-butadiene-styrene (ABS) copolymers have been prepared via an emulsion polymerization process. These functionalized ABS copolymers (ABS-g-GMA) were blended with poly(butylene terephthalate) (PBT). DMA result showed PBT was partially miscible with ABS and ABS-g-GMA, and DSC test further identified the introduction of GMA improved miscibility between PBT and ABS. Scanning electron microscopy (SEM) displayed a very good dispersion of ABS-g-GMA particles in the PBT matrix compared with the PBT/ABS blend when the content of GMA in PBT/ABS-g-GMA blends was relatively low (<8 wt% in ABS-g-GMA). The improvement of the disperse phase morphology was due to interfacial reactions between PBT chains end and epoxy groups of GMA, resulting in the formation of PBT-co-ABS copolymer. However, a coarse, non-spherical phase morphology was obtained when the disperse phase contained a high GMA content (≥8 wt%) because of cross-linking reaction between the functional groups of PBT and GMA. Rheological measurements further identified the reactions between PBT and GMA. Mechanical tests showed the presence of only a small amount of GMA (1 wt%) within the disperse phase was sufficient to induce a pronounced improvement of the impact and tensile properties of PBT blends. SEM results showed shear yielding of PBT matrix and cavitation of rubber particles were the major toughening mechanisms.     

New catalysts for poly(butylene terephthalate) synthesis. Part 3: effect of phosphate co-catalysts

An exhaustive study of the co-catalytic activity of phosphates on titanium and titanium/hafnium based catalytic systems in poly(butylene terephthalate) synthesis was conducted in order to investigate any improvement in the process and/or in the properties of the final polymer with respect to the industrially used titanium based catalyst. Small scale polymerisation and subsequent scale up in higher capacity reactors showed a strong co-catalytic effect of phosphates. A screening on model compounds showed NaH₂PO₄ to be the most active co-catalyst. The co-catalysts had a stronger effect on titanium with respect to hafnium. Decreases in polymerisation time and tetrahydrofuran formation were observed, which in turn can improve the productivity of the whole process. Moreover, the use of phosphate improved the thermal stability of the final polymers.     

Strain recovery of post-yield compressed semicrystalline poly(butylene terephthalate)

Cubic specimens of a semicrystalline poly(butylene terephthalate) (PBT) have been compressed up to post-yield deformation levels with a fast (3.0 × 10⁻² s⁻¹) and a slow (1.5 × 10⁻⁴ s⁻¹) strain rate at three different temperatures (25 °C, 45 °C, and 100 °C, i.e. below, close and above the glass transition temperature of the material, T_g, respectively). Differently from literature results reported for amorphous polymers, semicrystalline PBT shows that, after a post-yield deformation, recovery occurs also at temperatures higher than T_g, and that an irreversible deformation, ?_irr, is set in the material. The irreversible strain component has been evaluated as the residual deformation after a thermal treatment of 1 h at 180 °C.After unloading, isothermal strain recovery has been monitored for time periods of 1 h at various temperatures. From the obtained data, strain recovery master curves have been constructed by a time-temperature superposition scheme. The features of the recovery process for the various deformation conditions have been analysed. In particular, it appears that specimens deformed below T_g show a lower irreversible component, whereas, when deformed above T_g, they display a higher irreversible deformation and a slower recovery process. Moreover, the effect of deformation rate appears particularly marked for samples deformed above T_g.     

Phase separation in poly(butylene terephthalate)-based materials prepared by solid-state modification

The morphology of a series of poly(butylene terephthalate) (PBT)/fatty acid dimer diol (FADD)-based copolyesters prepared by solid-state modification (SSM) was studied. It was shown that in copolyesters containing less than 10 wt% FADD two different phases, i.e. a PBT crystalline phase and a PBT-rich amorphous phase, are present. The FADD residues were more or less homogeneously distributed throughout the interlamellar regions. For copolymers containing more than 10 wt% of FADD, a three-phase morphological model has to be used due to phase separation of a FADD-rich amorphous phase from the PBT-rich matrix, as confirmed by solid-state nuclear magnetic resonance spectroscopy and transmission electron microscopy. The final morphology was dependent on the morphology of the PBT/FADD-based physical mixtures prior to SSM. In addition, it was shown that FADD diffusion during SSM influences the final morphology.     

Post-yield compressed semicrystalline poly(butylene terephthalate): energy storage and release

Post yield deformation of semicrystalline poly(butylene terephthalate) (PBT) is studied by differential scanning calorimetry (DSC) measurements on compressed specimens after unloading. In particular, the effects of strain level, loading-unloading rate, and deformation temperature are analyzed. DSC traces indicate that a remarkable fraction of the mechanical work of deformation (in the range from 25 up to 62%) is stored in the material after unloading. Final strain dependence of stored energy values for specimens deformed up to 40% follows the general S-shaped trend observed for many amorphous and semicrystalline polymers. The ratio of the stored energy to the mechanical work of deformation (ΔU_ST/W) is decreasing as the final deformation level increases. For a given final strain level, the amount of energy stored in specimens deformed under T_g increases as either loading or unloading rates increase: in particular, both ΔU_ST and ΔU_ST/W values are linearly increasing with the logarithm of loading rate. On the other hand, energy storage for specimens deformed at T_g results to be practically independent from the loading rate. Moreover, as the deformation temperature increases from 25 to 100 °C, ΔU_ST values markedly decrease, while the ratio ΔU_ST/W is almost constant around an average value of about 51%.     

Stiffer and super-tough poly(butylene terephthalate) based blends by modification with phenoxy and maleated poly(ethylene-octene) copolymers

New super-tough poly(butylene terephthalate) (PBT) materials were obtained by melt blending PBT with both 20 wt% phenoxy (Ph) and 0-30 wt% maleic anhydride grafted poly(ethylene-octene) (mPEO) copolymers with different grafting levels. Ph was completely miscible in the PBT matrix. The presence of mPEO did not influence either the nature of the PBT-Ph matrix or the crystallization of PBT. The overall decrease in particle size and in interfacial tension upon grafting indicated that compatibilization had taken place. Super-tough (impact strength 23-fold that of the PBT) and stiffer PBT based blends were obtained at mPEO contents equal to or higher than 15%. The dependence of the critical inter-particle distance (τ_c), on both adhesion measured by means of the interfacial tension, and on the relation between the modulus of the matrix and that of the rubbery dispersed phase (E_m/E_d), is proposed.     

Morphological study on three kinds of two-dimensional spherulites of poly(butylene terephthalate) (PBT)

Three kinds of thin film specimens, each of which containing one of the three types of two-dimensional poly(butylene terephthalate) (PBT) spherulites (i: usual-positive type, ii: usual-negative type, and iii: unusual type), were prepared and studied mainly by transmission electron microscopy. It was confirmed that all these kinds of spherulites are made up of only the α-modification crystals, and the growth directions for usual-positive type, usual-negative type, and unusual type are the [010]^∗, ^∗, and ^∗ directions in the reciprocal lattice, respectively. Furthermore, the arrangement of unit cell in each type of the spherulites was determined. The relationships between the arrangements of unit cell and the types of each resulting spherulite are discussed.     

Processing and assessment of poly(butylene terephthalate) nanocomposites reinforced with oxidized single wall carbon nanotubes

Thermoplastic composites with carbon nanotubes (CNT) have a great potential as structural material because of their superior mechanical properties and ease of processing. The objective of this report is to evaluate the effect of oxidized single walled carbon nanotubes (oSWCNT) on the properties of poly(butylene terephthalate) (PBT) thermoplastic polymers, as a function of their weight content. The nanocomposites are obtained by introducing the oSWCNT into the reaction mixture whilst the synthesis of PBT. The polymers without and with carbon nanotubes were synthesised using an in situ polycondensation reaction process. Weight percentages ranging from 0.01 to 0.2 wt% of single walled nanotubes were dispersed in 1,4-butanediol (BD) by ultrasonication and ultrahigh speed stirring. After polycondensation the nanocomposites were extruded followed by injection moulding. The samples were characterised by thermal analysis, electron microscopy, dynamic-mechanical analysis, and tensile testing.The addition of only a small amount of oSWCNT was enough to improve the thermo-mechanical properties of the nanocomposites. The Young's modulus, tensile strength, and strain to failure increased with increasing amount from 0.01 to 0.1 wt% of CNT in the PBT matrix. However, when the content of CNT was increased from 0.1 to 0.2 wt%, the strength and the strain of the nanocomposites decreased slightly.     

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     

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     

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.     

聚对苯二甲酸甲二酯的热分解行为及其动力学研究

研究了惰性气氛下聚对苯二甲酸甲二酯(PMT)的非等温热分解行为及其动力学,并与聚对苯二甲酸丁二酯 (PBT)进行了对比。研究发现,PMT的热降解过程包括两个主要失重阶段,其热分解反应不是一级反应。第一阶段的起始分解温度较低是由于产物的分子链末端基中含有Br或Cl能催化聚合物的降解反应;第二阶段为分子链主体的热分解过程,由于分子链中苯环的密度较大,分子链的热稳定性比具有较低苯环密度的PBT要高。而PBT的降解失重过程仅为一个阶段,为一级反应。     

Melting behavior and crystallization kinetics of poly(butylene terephthalate‐co‐diethylene terephthalate) and poly(butylene terephthalate‐co‐triethylene terephthalate) copolyesters

The melting behavior of poly(butylene terephthalate‐co‐diethylene terephthalate) and poly(butylene terephthalate‐co‐triethylene terephthalate) copolymers was investigated by differential scanning calorimetry after isothermal crystallization from the melt. Multiple endotherms were found for all the samples, and attributed to the melting and recrystallization processes. By applying the Hoffman‐Weeks' method, the equilibrium melting temperatures of the copolymers under investigation were obtained. Two distinct peaks in the crystallization exothermic curve were observed for all the samples. Both of them appeared at higher times than that of PBT, indicating that the introduction of a comonomer decreased the crystallization rate. The observed dependence of this latter on composition was explained on the basis of the content of ether–oxygen atoms in diethylene and triethylene terephthalate units, and of the different sizes of these units. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3545–3551, 2001     

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     

聚对苯二甲酸丁二醇酯的化学扩链改性研究

以 2 ,2′ -双 ( 2 -唑啉 ) (BOZ)为扩链剂 ,对聚对苯二甲酸丁二醇酯 (PBT)进行扩链改性 ,考察了反应时间、扩链剂用量对扩链效果的影响 ,测试了扩链后PBT的热失重、力学性能和DSC。结果表明 ,BOZ的用量为 0 .44 % ,反应时间 3～ 5min ,PBT的最大扩链效率可达 72 .9% ,PBT的特性粘数从 0 .83dL/g提高到 1.2 1dL/ g ,扩链后PBT热稳定性和力学性能都得到提高。