Recycled poly(ethylene terephthalate)/linear low‐density polyethylene blends through physical processing

Poly(styrene‐ethylene/butylene‐styrene) (SEBS) was used as a compatibilizer to improve the thermal and mechanical properties of recycled poly(ethylene terephthalate)/linear low‐density polyethylene (R‐PET/LLDPE) blends. The blends compatibilized with 0–20 wt % SEBS were prepared by low‐temperature solid‐state extrusion. The effect of SEBS content was investigated using scanning electron microscope, differential scanning calorimeter, dynamic mechanical analysis (DMA), and mechanical property testing. Morphology observation showed that the addition of 10 wt % SEBS led to the deformation of dispersed phase from spherical to fibrous structure, and microfibrils were formed at the interface between two phases in the compatibilized blends. Both differential scanning calorimeter and DMA results revealed that the blend with 20 wt % SEBS showed better compatibility between PET and LLDPE than other blends studied. The addition of 20 wt % of SEBS obviously improved the crystallizibility of PET as well as the modulus of the blends. DMA analysis also showed that the interaction between SEBS and two other components enhanced at high temperature above 130°C. The impact strength of the blend with 20 wt % SEBS increased of 93.2% with respect to the blend without SEBS, accompanied by only a 28.7% tensile strength decrease. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Thermal properties and morphology of recycled poly(ethylene terephthalate)/maleic anhydride grafted linear low‐density polyethylene blends

Properties of recycled Poly(ethylene terephthalate) were greatly improved. Recycled PET was blended with LLDPE‐g‐MA by low‐temperature solid‐state extrusion. Mechanical properties of the blends were affected obviously by the added LLDPE‐g‐MA. Elongation at break reaches 352.8% when the blend contains 10 wt % LLDPE‐g‐MA. Crystallization behavior of PET phase was affected by LLDPE‐g‐MA content. Crystallinity of PET decreased with the increase of LLDPE‐g‐MA content. FTIR testified that maleic anhydride group in LLDPE‐g‐MA reacted with the end hydroxyl groups of PET and PET‐co‐LLDPE‐g‐MA copolymers were in situ synthesized. SEM micrographs display that LLDPE‐g‐MA phase and PET phase are incompatible and the compatibility of the blends can be improved by the forming of PET‐co‐LLDPE‐g‐MA copolymer. LLDPE‐g‐MA content was less, the LLDPE‐g‐MA phase dispersed in PET matrix fine. With the increase of LLDPE‐g‐MA content, the morphology of dispersed LLDPE‐g‐MA phase changed from spherule to cigar bar, then to irregular spherule. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Recyclability of In Situ Microfibrillar Poly(ethylene terephthalate)/High‐Density Polyethylene Blends

Repetitive processing was employed to assess the recyclability of in situ microfibrillar poly(ethylene terephthalate) (PET)/high‐density polyethylene (HDPE) blends which were fabricated through a “rectangular slit die extrusion–hot stretching–quenching” process. For comparison, the conventional PET/HDPE blends were also obtained using the same processing operation but without hot stretching. The morphological observation indicated that slit die extrusion and hot stretching successfully made the dispersed PET phase deform in situ into well‐defined microfibrils. The average diameter of the microfibrils increased with the processing cycles. The rheological properties obtained from the parallel‐plate dynamic rheometer suggested that the microfibrillar blends have higher viscosity and viscoelastic moduli (storage and loss moduli) as well as better flow stability than the conventional PET/HDPE blend. More importantly, with the increase in the processing cycles, an increase in yield strength and unchanged tensile modulus were observed for in situ microfibrillar blends, while a decrease in these properties for conventional blend, indicating that the in situ microfibrillar PET/HDPE blends have promising recycling potential.

     

Fine structure and physical properties of polyethylene/poly(ethylene terephthalate) bicomponent fibers in high‐speed spinning. I. Polyethylene sheath/poly(ethylene terephthalate) core fibers

The high‐speed melt spinning of sheath/core type bicomponent fibers was performed and the change of fiber structure with increasing take‐up velocity was investigated. Two kinds of polyethylene, high density and linear low density (HDPE, LLDPE) with melt flow rates (MFR) of 11 and 50, [HDPE(11), LLDPE(50)], and poly(ethylene terephthalate) (PET) were selected and two sets of sheath/core combinations [HDPE(11)/PET and LLDPE(50)/PET bicomponent fibers] were studied. The fiber structure formation and physical property effects on the take‐up velocities were investigated with birefringence, wide‐angle X‐ray diffraction, thermal analysis, tensile tests, and so forth. In the fiber structure formation of PE/PET, the PET component was developed but the PE components were suppressed in high‐speed spinning. The different kinds of PE had little affect on the fine structure formation of bicomponent fibers. The difference in the mechanical properties of the bicomponent fiber with the MFR was very small. The instability of the interface was shown above a take‐up velocity of 4 km/min, where the orientation‐induced crystallization of PET started. LLDPE(50)/PET has a larger difference in intrinsic viscosity and a higher stability of the interface compared to the HDPE(11)/PET bicomponent fibers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2254–2266, 2000     

Improved compatibility of high‐density polyethylene/poly(ethylene terephthalate) blend by the use of blocked isocyanate group

The blocked isocyanate group (BHI) was synthesized to improve the storage stability of HI (2‐hydroxyethyl methacrylate combined with isophorone diisocyanate) and characterized by Fourier transform infrared spectroscopy (FTIR). High‐density polyethylene grafted with the blocked isocyanate group (HDPE‐g‐BHI) was used as a reactive compatibilizer for an immiscible high‐density polyethylene/poly(ethylene terephthalate) (HDPE/PET) blend. A possible reactive compatibilization mechanism is that regenerated isocyanate groups of HDPE functionalized by BHI react with the hydroxyl and carboxyl groups of PET during melt blending. The HDPE‐g‐BHI/PET blend showed the smaller size of a dispersed phase compared to the HDPE/PET blend, indicating improved compatibility between HDPE and PET. This increased compatibility was due to the formation of an in situ graft copolymer, which was confirmed by dynamic mechanical analysis. Differential scanning calorimetry (DSC) analysis represented that there were few changes in the crystallinity for the continuous PET phase of the HDPE‐g‐BHI/PET blends, compared with those of the HDPE/PET blends at the same composition. Tensile strengths and elongations at the break of the HDPE‐g‐BHI/PET blends were greater than those of the HDPE/PET blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1017–1024, 2000     

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     

Uniaxial orientation and tensile properties of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blends

Amorphous films of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) (PET/PEN) blends with different blend ratios were uniaxially drawn by solid-state coextrusion and the structure development during solid state deformation was studied. As-prepared blends showed two T_gs. The lower T_g was ∼72 °C, independent of the blend ratio. In contrast, the higher T_g increased with increasing PEN content. Thus, the coextrusion was carried out around the higher T_g of the sample. At a given draw ratio of 5, which was close to the achievable maximum draw ratio, the tensile strength of the drawn samples from the initially amorphous state increased gradually with increasing PEN content. On the other hand, the tensile modulus was found to decrease initially, reaching a minimum at 40-60 wt% PEN, and then increased as the PEN content increased. The results indicate that we can get the drawn films with a moderate tensile modulus and a high tensile strength. The drawn samples from the blends containing 40-60 wt% of PEN showed a maximum elongation at break, and a maximum thermal shrinkage around 100 °C. Also, the degree of stress-induced crystallinity showed a broad minimum around the blend ratio of 50% of PEN. These morphological characteristics explained well the effects of blend ratio on the tensile modulus and strength of drawn PET/PEN blend films.     

Crystalline and thermal behavior of poly(ethylene terephthalate)/polyphenoxy blends

Poly(ethylene terephthalate) (PET)/polyphenoxy blends were prepared by melt blending. Crystalline and thermal behaviors of PET/polyphenoxy blends were verified by use of DSC. The experiment results show that the initial temperature, peak temperature, and ending temperature of cold crystallization increase with increasing phenoxy content. On the contrary, the onset melting temperature, finishing melting temperature, and peak temperature in the first heating and the secondary heating processes decrease with increasing phenoxy content. The crystallization enthalpy and melting enthalpy, as well as the crystallization rate, decrease with increasing phenoxy content. Avrami exponents of the blends are slightly higher than that of pure PET and almost independent of phenoxy content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 878–885, 2005     

In situ microfibrillar‐reinforced composites of isotactic polypropylene/recycled poly(ethylene terephthalate) system and effect of compatibilizer

Recycled poly(ethylene terephthalate) from waste bottles (hereafter, rPET) was used as an reinforcing material for isotactic polypropylene (iPP) based on the concept of in situ microfibrillar‐reinforced composites (iMFCs). Microfibers of rPET were successfully generated during melt‐extrusion and subsequent drawing and preserved in the final injection‐molded specimens. The effects of draw ratio, initial size of ground rPET flakes, and rPET content on morphological appearance of the extrudates and the as‐formed rPET fibers and mechanical properties of the as‐prepared iMFCs were investigated. The results showed that diameters of the as‐formed rPET fibers decreased with increasing draw ratio, and the initial size of ground rPET flakes did not affect the final diameters of the as‐formed rPET fibers nor the mechanical properties of the as‐prepared iMFCs. Flexural modulus, tensile modulus, and tensile strength of iPP/rPET iMFCs were improved by the presence of rPET microfibers and further improvement could be achieved by the addition of maleic anhydride‐grafted iPP (PP‐g‐MA), which was used as the compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1173–1181, 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     

Preparation and characterization of poly(ethylene terephthalate) powder‐filled high‐density polyethylene in the presence of silane coupling agents

Micron‐size crystalline particles of Poly(ethylene terephthalate) (PET), obtained from PET bottles by crystallization and grinding, were used as a filler in high‐density polyethylene (HDPE). The composite of PET particle‐filled HDPE was prepared by melt mixing at 190°C, which was well below the melting temperature of PET. Silane coupling agents (SCAs) were used to enhance the interaction between PET and HDPE in the composite. A chain extender (CE) and maleic anhydride (MA) were also used to provide further interaction with SCAs between these two materials. The ultimate tensile strength, especially at highest content 40% PET‐filled HDPE, and the impact strength of SCAs‐treated PET‐filled HDPE was found to be highly improved compared to untreated PET filling into HDPE. Dynamic mechanical analyses (DMA) demonstrated that T_g of the main matrix polyethylene was depressed from 3 to 10°C. Scanning electron microscopy (SEM) studies indicated a strong interaction between PET powder and HDPE when SCAs were present in the system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 827–835, 2001     

A preliminary study of blends of bisphenol a polycarbonate and poly(ethylene terephthalate)

The microstructure of blends of bisphenol A polycarbonate (PC), and poly(ethylene terepthalate) (PETP) has been studied by solvent extraction, infrared spectrophotometry, differential scanning calorimetry and dynamic mechanical thermal analysis. The blends appear to contain two amorphous phases over the whole composition range. The tensile behaviour and the Charpy impact strength of some of the blends have been determined, before and after heat treatment at 125°C for 18 hours. Improved performance of the blends, compared with that of the homopolymers PC and PETP, has been demonstrated.     

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     

Spinning and properties of poly(ethylene terephthalate)/organomontmorillonite nanocomposite fibers

By in situ polycondensation, a intercalated poly(ethylene terephthalate)/organomontmorillonite nanocomposite was prepared after montmorillonite (MMT) had been treated with a water‐soluble polymer. This nanocomposite was produced to fibers through melt spinning. The resulting nanocomposite fibers were characterized by X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and transmission electron microscopy (TEM). The interlayer distance of MMT dispersed in the nanocomposite fibers was further enlarged because of strong shear stress during processing of melt spinning. This was confirmed by XRD test and TEM images. DSC test results showed that incorporation of MMT accelerated the crystallization of poly(ethylene terephthalate) (PET), but the crystallinity of the drawn fibers just had a little increasing compared with that of neat PET drawn fibers. Also compared with pure PET drawn fibers, tensile strength at 5% elongation and thermal stability of the nanocomposite fibers were improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1443–1447, 2005     

New epoxy resins based on recycled poly(ethylene terephthalate) as organic coatings

Glycolysis of poly(ethylene terephthalate), PET, waste using trimethylol propane (TMP), triethanolamine (TEA), diethylene glycol (DEG) and diethanolamine (DEA) was used to produce suitable hydroxy-oligomers for epoxy. The glycolyzed products were reacted with epichlorohydrine to prepare a series of di- and tetraglycidyl epoxy resins with different molecular weights. The glycolysis was carried out in presence of manganese acetate as a catalyst at normal and high pressure in presence and absence of xylene at 210 °C. The produced resins were cured with different mole ratios of 1-(2-amino ethyl) piprazine as curing agent at room temperature. The mechanical properties of the cured epoxy resins were evaluated. The chemical resistances of the cured resins were evaluated through salt spray resistance, hot water, solvents, acid and alkali resistance measurements. The data indicate that the cured epoxy resins based on glycolyzed oligomer of PET and DEA have excellent chemical resistances as organic coatings among other cured resins.     

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     

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。     

Heterogeneous blends of recycled poly(ethylene terephthalate) with impact modifiers: phase structure and tensile creep

Several types of photomicrographs have concurrently shown that impact modifiers (IMs) form particles (on a micrometre scale) which are evenly dispersed in a recycled poly(ethylene terephthalate) (PET) matrix; their adhesion to the latter is high enough that fracture surfaces (produced in liquid nitrogen) do not follow the interface. An essential part of the tensile creep of PET corresponds to the elastic time‐independent component; the time‐dependent component is rather limited, even if relatively high stresses are applied. Thus, the tensile compliance of PET is virtually independent of the applied stress, which indicates linear viscoelastic behaviour. The compliance of PET/IM blends (93/7, 90/10, 85/15 (by weight)) grows with the IM content and its time‐dependence becomes more visible. The effects of the two types of IM used in this study seem to be practically identical from the viewpoint of dimensional stability of the blends. The logarithm of compliance grows with the logarithm of time faster than linearly, and this tendency becomes more apparent with increasing fraction of IM. Even if the strain‐induced free volume is taken into account, a noticeable upswing of the compliance for longer creep periods (t > 1000 min) is evident. This cannot be interpreted as a consequence of the flow, because the recovery following the creep has proved the complete reversibility of the previous deformation. A simple empirical equation is proposed, which provides a plausible prediction of the creep behaviour of PET with dispersed impact modifiers. Copyright © 2004 Society of Chemical Industry     

玻璃纤维增强回收聚对苯二甲酸乙二醇酯复合材料的力学性能

用熔融共混制备了玻璃纤维（GF）增强的回收聚对苯二甲酸乙二醇酯（rPET）复合材料,研究了复合材料的力学性能并进一步利用Halpin-Tsai模型、Krenchel-COX模型和Kelly-Tyson模型探讨了GF的近程和远程结构与复合材料性能间的关系。结果表明,GF对rPET具有较为显著的增强、增韧效果。当玻璃纤维含量为30 %(质量分数,下同)时,复合材料的冲击强度、拉伸强度以及弯曲强度分别提高了245 %、113 %以及84 %;长径比和取向度是影响GF改性rPET复合材料性能的重要结构参数;Halpin-Tsai方程能够较好地描述rPET/GF复合材料中GF的有效长径比;而相比于Krenchel-COX方程,由Kelly-Tyson方程获得的GF的取向度更接近实验结果。