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     

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。     

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     

Microstructure and crystallization of melt‐mixed poly(ethylene terephthalate)/poly(ethylene isophthalate) blends

Physical blends of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI), abbreviated PET/PEI (80/20) blends, and of PET and a random poly(ethylene terephthalate‐co‐isophthalate) copolymer containing 40% ethylene isophthalate (PET₆₀I₄₀), abbreviated PET/PET₆₀I₄₀ (50/50) blends, were melt‐mixed at 270°C for different reactive blending times to give a series of copolymers containing 20 mol % of ethylene isophthalic units with different degrees of randomness. ¹³C‐NMR spectroscopy precisely determined the microstructure of the blends. The thermal and mechanical properties of the blends were evaluated by DSC and tensile assays, and the obtained results were compared with those obtained for PET and a statistically random PETI copolymer with the same composition. The microstructure of the blends gradually changed from a physical blend into a block copolymer, and finally into a random copolymer with the advance of transreaction time. The melting temperature and enthalpy of the blends decreased with the progress of melt‐mixing. Isothermal crystallization studies carried out on molten samples revealed the same trend for the crystallization rate. The effect of reaction time on crystallizability was more pronounced in the case of the PET/PET₆₀I₄₀ (50/50) blends. The Young's modulus of the melt‐mixed blends was comparable to that of PET, whereas the maximum tensile stress decreased with respect to that of PET. All blend samples showed a noticeable brittleness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3076–3086, 2003     

Properties of uncompatibilized and compatibilized poly(butylene terephthalate)–LLDPE blends

In this work, blends of poly(butylene terephthalate) (PBT) and linear low‐density polyethylene (LLDPE) were prepared. LLDPE was used as an impact modifier. Since the system was found to be incompatible, compatibilization was sought for by the addition of the following two types of functionalized polyethylene: ethylene vinylacetate copolymer (EVA) and maleic anhydride‐grafted EVA copolymer (EVA‐g‐MAH). The effects of the compatibilizers on the rheological and mechanical properties of the blends have been also quantitatively investigated. The impact strength of the PBT–LLDPE binary blends slightly increased at a lower concentration of LLDPE but increased remarkably above a concentration of 60 wt % of LLDPE. The morphology of the blends showed that the LLDPE particles had dispersed in the PBT matrix below 40 wt % of LLDPE, while, at 60 wt % of LLDPE, a co‐continuous morphology was obtained, which could explain the increase of the impact strength of the blend. Generally, the mechanical strength was decreased by adding LLDPE to PBT. Addition of EVA or EVA‐g‐MAH as a compatibilizer to PBT–LLDPE (70/30) blend considerably improved the impact strength of the blend without significantly sacrificing the tensile and the flexural strength. More improvement in those mechanical properties was observed in the case of the EVA‐g‐MAH system than for the EVA system. A larger viscosity increase was also observed in the case of the EVA‐g‐MAH than EVA. This may be due to interaction of the EVA‐g‐MAH with PBT. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 989–997, 1999     

Chain extension of poly(ethylene terephthalate) by reactive blending using diepoxides

Molecular weight increase via chain extension reactions of poly(ethylene terephthalate) with commercially available diepoxides was studied in a custom‐made laboratory scale reactor and a Brabender rheomixer under reactive blending conditions. The products were characterized by carboxylic end group analysis, intrinsic viscosity, and differential scanning calorimetry. PET was effectively modified in the laboratory‐scale reactor using cyclic diepoxides because the resulting polymers show intrinsic viscosities that are comparable to virgin PET (0.68–0.75 dL/g vs. 0.74 dL/g) and much higher than processed PET (0.55), while carboxyl contents were reduced to a third of that of the virgin PET. Diglycidyl ethers produced polymers displaying decreased viscosity values, increased carboxyl content, and lower melting points. Low concentrations of extender and short reaction times generally favored chain extension. In addition, purging with nitrogen resulted in chain extended polymers having the highest values of intrinsic viscosity ([η] = 0.79, 0.82). Similar trends were observed with modified products in the rheomixer having somewhat smaller viscosity values, larger carboxyl contents, and increased melting points. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2121–2127, 1999     

Rheological behavior of polyester blend and mechanical properties of the polypropylene–polyester blend fibers

The article deals with method of preparation, rheological properties, phase structure, and morphology of binary blend of poly(ethylene terephthalate) (PET)/poly(butylene terephthalate) (PBT) and ternary blends of polypropylene (PP)/(PET/PBT). The ternary blend of PET/PBT (PES) containing 30 wt % of PP is used as a final polymer additive (FPA) for blending with PP and subsequent spinning. In addition commercial montane (polyester) wax Licowax E (LiE) was used as a compatibilizer for spinning process enhancement. The PP/PES blend fibers containing 8 wt % of polyester as dispersed phase were prepared in a two‐step procedure: preparation of FPA using laboratory twin‐screw extruder and spinning of the PP/PES blend fibers after blending PP and FPA, using a laboratory spinning equipment. DSC analysis was used for investigation of the phase structure of the PES components and selected blends. Finally, the mechanical properties of the blend fibers were analyzed. It has been found that viscosity of the PET/PBT blends is strongly influenced by the presence of the major component. In addition, the major component suppresses crystallinity of the minor component phase up to a concentration of 30 wt %. PBT as major component in dispersed PES phase increases viscosity of the PET/PBT blend melts and increases the tensile strength of the PP/PES blend fibers. The impact of the compatibilizer on the uniformity of phase dispersion of PP/PES blend fibers was demonstrated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4222–4227, 2006     

Improvement of compatibility of poly(ethylene terephthalate) and poly(ethylene octene) blends by γ‐irradiation

Blends of poly(ethylene terephthalate) (PET) and poly(ethylene octene) (POE) were prepared by melt blending with various amounts of trimethylolpropane triacylate (TMPTA). The mechanical properties, phase morphologies, and gel fractions at various absorbed doses of γ‐irradiation have been investigated. It was found that the toughness of blends was enhanced effectively after irradiation as well as the tensile properties. The elongation at break for all studied PET/POE blends (POE being up to 15 wt %) with 2 wt % TMPTA reached 250–400% at most absorbed doses of γ‐irradiation, approximately 50–80 times of those of untreated PET/POE blends. The impact strength of PET/POE (85/15 wt/wt) blends with 2 wt % TMPTA irradiated with as little as 30 kGy absorbed dose exceeded 17 kJ/m², being approximately 3.4 times of those of untreated blends. The improvement of the mechanical properties was supported by the morphology changes. Scanning electron microscope images of fracture surfaces showed a smaller dispersed phase and more indistinct inter‐phase boundaries in the irradiated blends. This indicates increased compatibility of PET and POE in the PET/POE blends. The changes of the morphologies and the enhancement of the mechanical properties were ascribed to the enhanced inter‐phase boundaries by the formation of complex graft structures confirmed by the results of the gelation extraction and Fourier Transform Infrared analyses. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of poly(ethylene glycol) on the solid‐state polymerization of poly(ethylene terephthalate)

Poly(ethylene glycol) (PEG) and end‐capped poly(ethylene glycol) (poly(ethylene glycol) dimethyl ether (PEGDME)) of number average molecular weight 1000 g mol^?1 was melt blended with poly(ethylene terephthalate) (PET) oligomer. NMR, DSC and WAXS techniques characterized the structure and morphology of the blends. Both these samples show reduction in T_g and similar crystallization behavior. Solid‐state polymerization (SSP) was performed on these blend samples using Sb₂O₃ as catalyst under reduced pressure at temperatures below the melting point of the samples. Inherent viscosity data indicate that for the blend sample with PEG there is enhancement of SSP rate, while for the sample with PEGDME the SSP rate is suppressed. NMR data showed that PEG is incorporated into the PET chain, while PEGDME does not react with PET. Copyright © 2005 Society of Chemical Industry     

Influence of the degree of grafting on the morphology and mechanical properties of blends of poly(butylene terephthalate) and glycidyl methacrylate grafted poly(ethylene‐co‐propylene) (EPR)

Poly(ethylene‐co‐propylene) (EPR) was functionalized to varying degrees with glycidyl methacrylate (GMA) by melt grafting processes. The EPR‐graft‐GMA elastomers were used to toughen poly(butylene terephthalate) (PBT). Results showed that the grafting degree strongly influenced the morphology and mechanical properties of PBT/EPR‐graft‐GMA blends. Compatibilization reactions between the carboxyl and/or hydroxyl of PBT and epoxy groups of EPR‐graft‐GMA induced smaller dispersed phase sizes and uniform dispersed phase distributions. However, higher degrees of grafting (>1.3) and dispersed phase contents (>10 wt%) led to higher viscosities and severe crosslinking reactions in PBT/EPR‐graft‐GMA blends, resulting in larger dispersed domains of PBT blends. Consistent with the change in morphology, the impact strength of the PBT blends increased with the increase in EPR‐graft‐GMA degrees of grafting for the same dispersion phase content when the degree of grafting was below 1.8. However, PBT/EPR‐graft‐GMA1.8 displayed much lower impact strength in the ductile region than a comparable PBT/EPR‐graft‐GMA1.3 blend (1.3 indicates degree of grafting). Morphology and mechanical results showed that EPR‐graft‐GMA 1.3 was more suitable in improving the toughness of PBT. SEM results showed that the shear yielding properties of the PBT matrix and cavitation of rubber particles were major toughening mechanisms. Copyright © 2006 Society of Chemical Industry     

PEN/PET共混物结晶行为研究

用差示扫描量热法(DSC)研究了不同共混比例PEN/PET共混物的熔体结晶行为,并进行了等温结晶动力学测定。结果表明:随着两种组分向中间比例(50/50)靠近,共混物的熔融温度越低,结晶速率也越慢。     

Mechanical properties of poly(ethylene terephthalate) modified with functionalized polymers

This study examined the effect of blending poly(ethylene terephthalate) (PET) with 5% of a functionalized polymer. The blends were characterized by particle size and size distribution, unnotched tensile behavior, toughness, and notch sensitivity. The improved properties of blends that incorporated a functionalized elastomer were consistent with in situ formation of a graft copolymer by reaction with PET end groups. Triblock copolymers were examined that had styrene end blocks and an ethylene/butylene midblock (SEBS) with grafted maleic anhydride. The present study extended previous investigations that focused on level of grafting to examine the effects of component molecular weight and PET hydroxyl‐to‐carboxyl end‐group ratio. Increasing the molecular weight of the SEBS and decreasing the hydroxyl‐to‐carboxyl ratio of the PET increased the effectiveness of the SEBS. In addition, a mix of an unfunctionalized SEBS with a functionalized SEBS was more effective than a single SEBS with the same total anhydride content. The same elastomers were the most effective for modifying a lower molecular weight PET (intrinsic viscosity 0.73) and a higher molecular weight PET (intrinsic viscosity 0.95). Some functionalized polypropylenes included in the study did not enhance the properties of PET. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 203–219, 1999     

Compatibility in immiscible polysulfone/poly(ethylene terephthalate) blends

Polysulfone (PSU)/poly(ethylene terephthalate) (PET) blends were obtained by direct injection molding across the composition range. Their phase behavior, thermal properties, morphology, and mechanical properties were measured. The blends were composed of a pure PSU amorphous phase and either a pure PET phase in PSU‐poor blends, or a PET‐rich phase with some dissolved PSU in PSU‐rich blends. The morphology of the dispersed phase was mostly spherical with some elongated particles in the PET‐rich blends. A slight synergistic behavior was observed in the Young's modulus, mainly in the 90/10 blend, which is probably due to orientation effects. The presence of some broken particles indicated some interfacial adhesion. The ductility values were approximately linear with composition. This was generally the case in PSU‐rich blends, and was attributed to the higher level of PSU in the PET‐rich phase. Although embrittlement was seen in blends with 30% of the second component, the ductility of the two pure components did not significantly decrease after annealing due to the presence of low amounts (up to 10%) of another component of the blend. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2193–2200, 2004     

Dispersion of nanoclays with poly(ethylene terephthalate) by melt blending and solid state polymerization

Melt intercalation of clay with poly(ethylene terephthalate; PET) was investigated in terms of PET chain mobilities, natures of clay modifiers, their affinities with PET, and nanocomposite solid state polymerization (SSP). Twin screw extrusion was used to melt blend PET resins with intrinsic viscosities of 0.48, 0.63, and 0.74 dL/g with organically modified Cloisite 10A, 15A, and 30B montmorillonite clays. Clay addition caused significant molecular weight reductions in the extruded PET nanocomposites. Rates of SSP decreased and crystallization rates increased in the presence of clay particles. Cloisite 15A blends showed no basal spacing changes, whereas the basal spacings of Cloisite 10A and Cloisite 30B nanocomposites increased after melt extrusion, indicating the presence of intercalated nanostructures. After SSP these nanocomposites also exhibited new lower angle X‐ray diffraction peaks, indicating further expansion of their basal spacings. Greatest changes were seen for nanocomposites prepared from the lowest molecular weight PET and Cloisite 30B, indicating its greater affinity with PET and that shorter more mobile PET chains were better able to enter its galleries and increase basal spacing. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Study on in situ reinforcing and toughening of a semiflexible thermotropic copolyesteramide in PBT/PA66 blends

Ternary in situ composites based on poly(butylene terephthalate) (PBT), polyamide 66 (PA66), and semixflexible liquid crystalline polymer (LCP) were systematically investigated. The LCP used was an ABA30/PET liquid crystalline copolyesteramide based on 30 mol % of p‐aminobenzoic acid (ABA) and 70 mol % of poly(ethylene terephthalate) (PET). The specimens for thermal and rheological measurements were prepared by batch mixing, while samples for mechanical tests were prepared by injection molding. The results showed that the melting temperatures of the PBT and PA66 phases tend to decrease with increasing LCP addition. They also shifted toward each other due to the compatibilization of the LCP. The torque measurements showed that the ternary blends exhibited an apparent maximum near 2.5–5 wt % LCP. Thereafter, the viscosity of the blends decreased dramatically at higher LCP concentrations. Furthermore, the torque curves versus the PA66 composition showed that the binary PBT/PA66 blends can be classified as negative deviation blends (NDBs). The PBT/PA66/LCP blends containing up to 15 wt % LCP were termed as positive deviation blends (PDBs), while the blends with the LCP ≥25 wt % exhibited an NDB behavior. Finally, the tensile tests showed that the stiffness and tensile strength of ternary in situ composites were generally improved with increasing LCP content. The impact strength of ternary composites initially increased by the LCP addition, then deteriorated when the LCP content was higher than 10 wt %. The correlation between the mechanical properties and morphology of the blends is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1975–1988, 2000     

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.     

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.     

Properties of poly(butylene terephthalate) chain‐extended by epoxycyclohexyl polyhedral oligomeric silsesquioxane

Epoxycyclohexyl polyhedral oligomeric silsesquioxane (epoxy–POSS) was used to prepare a chain‐extended poly(butylene terephthalate) (PBT) with a twin‐screw extruder. The effect of epoxy–POSS on the melt flow index, mechanical properties, rheological behavior, and thermal properties of chain‐extended PBT was investigated. PBT had an intrinsic viscosity of 1.1 dL/g and a carboxy1 content of 21.6 equiv/10⁶ g, but the PBT chain‐extended with 2 wt % epoxy–POSS had an intrinsic viscosity of 1.7 dL/g and a carboxy1 content lower than 7 equiv/10⁶ g. After the addition of epoxy–POSS, the melt flow index of PBT dramatically decreased, the elongation at break increased greatly, the tensile strength increased slightly, and the thermal stability was also improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of functionalized copolymers and their compatibilization effects on acrylonitrile butadiene styrene/poly(butylene terephthalate) blends

In this study, the copolymers of methyl methacrylate-co-glycidyl methacrylate (MGD) with different epoxy contents and molecular weights, the styrene-co-glycidyl methacrylate (SGD) and methyl methacrylate-co-maleic anhydride (MAD) were synthesized. The synthesized copolymers, styrene-co-maleic anhydride (SMA) and styrene-acrylonitrile-co-glycidyl methacrylate (SAG) were used as compatibilizers to enhance the impact strength of the acrylonitrile butadiene styrene/poly(butylene terephthalate) (ABS/PBT). The effects of differences in the structure, reactive group type, and molecular weight of the compatibilizers on the mechanical properties, phase morphology, melt viscosity, thermal stability, and melting temperature of the blend were studied. The results showed that functionalized copolymers were successfully synthesized with high monomer conversions. Addition of the functionalized copolymers increased melt viscosity but did not considerably affect thermal stability, tensile strength, flexural strength and melting temperature of the ABS/PBT blends. The compatibilizers improved the dispersion of the PBT phase and prevented brittle fracture, thereby increasing the impact strength of the blend. Among the studied compositions, the ABS/PBT/MGD-5 blend exhibited the highest impact strength of 25.8 kJ/m² and an appropriate melt flow index of 19.1 g/10 minutes. The compatibilizer should have an appropriate molecular weight to improve the interface bonding force. Regarding the melting viscosity, the reactive group content and compatibilizer dosage should be adjusted to ensure high impact strength.     

The interchange reaction between poly(ethylene terephthalate) and poly(m‐xylylene adipamide)

The interchange reaction in blends of poly(ethylene terephthalate) (PET) and poly(m‐xylylene adipamide) (MXD6) has been characterized in terms of changes observed in spectra obtained with a 600‐MHz ¹H‐NMR. The selective degradation of PET components in the blends was carried out in the NMR tubes prior to evaluation. Results indicate that there is no chemical reaction between the PET and MXD6 in the absence of sodium p‐toluenesulfonate catalyst. The presence of the catalyst activates the interchange reaction between these two resins. A mathematical method was applied to calculate the degree of randomness of PET‐MXD6 copolymer. In addition, the reaction degree was found to be affected by exposure temperature, time, shear rate, and catalyst concentration. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009