Modification of poly(ethylene terephthalate) (PET) using linoleic acid for oxygen barrier improvement: Impact of processing methods

Poly(ethylene terephthalate) (PET) is commonly used in the packaging industry; however, there is considerable interest in reducing the rate of oxygen permeation through PET to extend product shelf life. One method being employed to improve oxygen barrier is the introduction of reactive compounds to bind the oxygen permeating through the polymer. This work investigates a naturally occurring oxygen scavenger, linoleic acid (LA), which was incorporated within blown PET bottles using two different processing schemes. The LA was incorporated within PET at 0.5% by weight using both by blending and reaction of carboxyl end of LA and hydroxyl end of PET. The effect of LA on the thermal, mechanical properties, and oxygen permeation were determined. There was a decrease in oxygen permeability for the PET/LA samples with little change in physical properties relative to base PET. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45023.     

Separation and concentration of bilberry impact aroma compound from dilute model solution by pervaporation

BACKGROUND: In the present work, the flavor compounds of natural juice of bilberries were qualitatively analyzed by GC‐MS, leading to the identification of trans‐Hex‐2‐en‐1‐ol as one of the major ‘impact aroma’ compounds of this fruit. The pervaporation of trans‐Hex‐2‐en‐1‐ol from diluted aqueous solutions was studied using commercial polydimethylsiloxane (PDMS) capillary membranes. The influences of solvent composition (water/ethanol mixtures), initial concentration of the aroma compound, flow rate and temperature of the feed were studied. RESULTS: High selectivity of the PDMS membrane towards the aroma compound was obtained, leading to enrichment factors in the range 100 < β < 200. Mass transfer resistance was found to be located in the pervaporation membrane. Experimental data showed a linear dependency of the permeation flux of trans‐Hex‐2‐en‐1‐ol on the differences in partial pressures of the compound across the pervaporation membrane. The permeability coefficient of the PDMS membrane to the transport of trans‐Hex‐2‐en‐1‐ol was calculated as P_{m, Hex}(50 °C) = 7.62 × 10^?11 mol m^?1 s^?1 Pa^?1. CONCLUSION: The membrane used was found to be very selective toward trans‐Hex‐2‐en‐1‐ol. A model based on the solution‐diffusion mechanism was applied. The mass transfer parameters needed for the design of a pervaporation process for aroma compound recovery were obtained. Copyright © 2008 Society of Chemical Industry     

Characterization of Aroma-Active Compounds in Iranian cv. Mari Olive Oil by Aroma Extract Dilution Analysis and GC–MS-Olfactometry

Aroma, aroma‐active compounds and fatty acid profiles of Iranian olive oil obtained from the cv. Mari were investigated for the first time in the current study. Aroma extracts were isolated from the oil by using a purge and trap extraction system and their compositions were analyzed by gas chromatography‐mass spectrometry‐olfactometry (GC–MS‐O). A total of 35 aroma compounds comprising alcohols, aldehydes, acids, esters, ketones, terpenes and volatile phenols were identified and quantified in the assayed samples. Aldehydes were present at the highest levels, followed by ketones and alcohols. (E)‐2‐Hexenal was quantitatively (1589 µg kg^?1) the main aroma compound in the analyzed oils, followed by hexanal and (E)‐2‐heptenal. The aroma‐active volatiles were elucidated in the aromatic extract by applying aroma extract dilution analysis (AEDA). The results of AEDA revealed 17 aroma‐active compounds. Under these condition it was possible to completely identify 16 of these compounds. Regarding to the flavor dilution (FD) factor, the most potent odorants with the highest FD factor were (E)‐2‐hexenal (512), followed by hexanal, 6‐methyl‐5‐hepten‐2‐one, (E)‐2‐decenal and one unknown compound (LRI = 1871). The fatty acid profile of the tested oils was composed of thirteen compounds. Oleic acid was the main fatty acid (76.01 %) followed by palmitic acid.     

The thermal,optical, flame retardant,and morphological consequence of embedding diacid‐capped ZnO into the recycled PET matrix

We extended our work to a fast and facile nanocomposites (NCs) manufacturing by incorporation of ZnO nanoparticles (NPs) on to a recycled poly(ethylene terephthalate) PET as a polymer matrix prepared by a dissolution/reprecipitation method. The surface of ZnO NPs was functionalized with synthesized optically active diacid containing alanine amino acid. Organo‐modified NPs which provided using solution blending technique through ultrasonic irradiation, were embedded into recycled PET. PET@ZnO/DA NCs containing different loadings of functionalized NPs (1, 3, 5 wt %) were investigated by thermal gravimetric analysis, field emission scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy and UV–visible spectroscopy. Morphological studies revealed uniformly dispersed ZnO/DA NPs in the polymer matrix. The crystalline nature of PET slightly improved as a function of the NPs concentration. Char yield in TGA and LOI values indicated that the obtained NCs were capable of exhibiting flame retardant properties. The NCs were found to exhibit more absorbance in the UV and visible region in compare to the neat PET. The effect of ultrasonication in different solvent on the morphology of the recycled polymer particle was also studied. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43433.     

PET recycling: Evaluation of the solid state polymerization process

Many studies have been carried out to make bottle‐to‐bottle recycling feasible. One of the difficulties found is the decrease in the polymer's molar mass, which damages the injection blow molding process. A method usually employed to increase the molar mass of virgin PET consists of solid‐state polymerization (SSP). In this work, we studied the SSP process applied to post‐consumer recycled PET by analyzing the inherent viscosity and amount of carboxylic end groups, and the results of dynamic flow rheometry. Although the results show that the recycling process decreases polymer molar mass, and this indicates degradative processes, SSP was successful in increasing molar mass in post‐consumer recycled PET. This made feasible bottle‐to‐bottle recycling. In addition, the parallel plate rheometry technique was powerful in assessing the degradative process and, therefore, that the SSP process was successful. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Chain extension of recycled poly(ethylene terephthalate) with 2,2′‐(1,4‐phenylene)bis(2‐oxazoline)

The present work provides improved recycled high molecular weight poly(ethylene terephthalate) (PET) by chain extension using 2,2′‐(1,4‐phenylene)bis(2‐oxazoline) (PBO) as the chain extender. PBO is a very reactive compound toward macromolecules containing carboxyl end groups but not hydroxyl end groups. In the case of PET, where both species are present, for even better results, phthalic anhydride (PA) was added in the initial sample, before the addition of PBO. With this technique, we succeeded in increasing the carboxyl groups by reacting PA with the hydroxyl terminals of the starting polymer. From this modification of the initial PET sample, PBO was proved an even more effective chain extender. So, starting from a recycled PET with intrinsic viscosity [η] = 0.78, which would be [η] = 0.69 after the aforementioned treatment without a chain extender or M̄_n = 19,800, we prepared a PET grade having [η] = 0.85 or M̄_n = 25,600 within about 5 min. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2206–2211, 2000     

Functional barriers in PET recycled bottles. Part I. Determination of diffusion coefficients in bioriented PET with and without contact with food simulants

A major outcome for recycled plastics consists of making food packaging materials. However, any contamination of collected plastics with chemicals may then be of concern for public health. A solution to mind migration is to use a layer of virgin polymer, named functional barrier, intercalated between the recycled layer and the food. This article aims to provide experimental values of diffusion coefficients (D) of model pollutants (surrogates) in poly(ethylene terephthalate) (PET) to be used for modeling migration through functional barriers. Diffusion coefficients of a large set of surrogates at low concentrations in PET were measured in various conditions. A solid‐to‐solid diffusion test was designed to avoid the use of a solvent that may induce plasticizing of the material and partitioning effects at the interface. Using [Log D = f(molecular weight)] correlations, the values of diffusion coefficients and activation energies of the surrogates measured by this method were shown to be consistent with the literature data obtained for gases, in permeation experiments, where no plasticization occurred. Migration from PET into food simulants was then studied. Migration into an aqueous medium is largely influenced by the solubility of the surrogates, the less soluble ones being not detected, despite high D values. With ethanol solvent, there were no partitioning effects, and the high plasticization effect of PET by ethanol considerably increases the apparent diffusion coefficients. The effects of temperature and plasticization on the relationship between diffusion coefficients and molecular weight are discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2845–2858, 2004     

Analysing metals in bottle‐grade poly(ethylene terephthalate) by X‐ray fluorescence spectrometry

After a rigorous cleaning process, recycled food‐grade poly(ethylene terephthalate) (PET), can be mixed with virgin PET resin in different concentrations and used for packaging of soft drinks. Therefore, it is important to have an experimental method to distinguish the presence of recycled polymer in a batch and to check its “true quality.” One of the issues to be verified is the presence of inorganic contaminants due to the recycling process. X‐ray fluorescence technique is one alternative for this kind of analysis. The results obtained in this work show that bottle‐grade PET samples (PET‐btg) are made either via direct esterification or by a transesterification process. Samples that were subjected to thermo‐mechanical processings (superclean® processing, PET‐btg blends processed in our laboratory and soft drink PET packaging) present Fe Kα emission lines with higher intensities than those presented by virgin bottle‐grade PET. After applying principal component analysis, it can be concluded that Fe is an intrinsic contaminant after the recycling process, furnishing a way to indicate class separations of PET‐btg. A calibration and validation partial least squares model was constructed to predict the weight percent of post‐consumption bottle‐grade PET in commercial PET samples. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

再生聚酯直纺涤纶工业丝成套设备技术探讨

采用回收聚酯(PET)瓶片,通过液相增黏直接纺丝生产涤纶工业丝,探讨了再生聚酯直纺涤纶工业丝的成套设备和工艺技术。结果表明:对干燥设备和螺杆挤压机进行改造,利用双级熔体预过滤器和液相增黏系统,聚酯瓶片再生增黏后特性黏数可达(0.85±0.01)dL/g;该成套设备的关键是采用单轴式液相增黏反应器;调整纺丝和拉伸工艺,直接纺丝生产的涤纶工业丝线密度为1 189 dtex,断裂强度为7.98 cN/dtex,断裂伸长率为14.66%,达到了常规固相增黏法生产的涤纶工业丝的性能指标。     

Expanding the application field of post‐consumer poly(ethylene terephthalate) through structural modification by reactive blending

With the aim of up‐grading the material properties of post‐consumer PET, making them suitable for extrusion of thermoformable thick sheets, a series of polyepoxy chain extenders have been comparatively evaluated as melt viscosity modifiers for a toughened compatibilized blend containing up to 80 wt % of bottle‐grade post‐consumer recycled poly(ethylene terephtalate) (r‐PET). Combinations of a commercial modifier with pentaerythritol were also successfully employed to cause simultaneous hyperbranching and controlled chain scission, thereby modifying the melt rheology of the material without excessively increasing the molecular weight, as highlighted by common technological melt viscosity measurements such as online torque and off‐line melt flow rate (MFR). Since the high melt fluidity of PET plays a critical role on its flame resistance, the combined effect of chain extenders and halogen‐free phosphorated additives on the fire resistance of the modified toughened blends was also investigated. Preliminary results indicate that the chemical reactions among polymer and additives must be taken into careful account to prevent unfavorable effects on the ultimate melt rheology and mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40881.     

Chain extension and degradation during reactive processing of PET in the presence of triphenyl phosphite

Poly(ethylene terephthalate) (PET) is chemically degraded during processing and/or using by a number of sources including temperature, humidity, and ultraviolet radiation. As a consequence, a large loss in engineering properties is observed when PET products are recycled. To overcome this problem, various types of chain extenders were developed in an attempt to recover the polymer molecular sizes by chemical reactions during processing. This work investigates the use of triphenyl phosphite (TPP) as a chain extender of virgin and recycled PET. Compounds with 1 and 3% of TPP were prepared and processed under various conditions using a torque rheometer. An increase in torque during mixing was associated with chain extension reactions whereas the observed decrease in torque afterwards was due to chemical degradation. The optimum processing conditions were reached (260°C, 1% chain extender), with a maximum in chain extension and a minimum in subsequent degradation. An important finding of this work was that the chemical degradation of chain extended PET occurs very easily during storage and it was considered to be a result of the influence of by‐products of TPP reaction with PET. The extraction of these products with acetone was shown to be quite effective, with a considerable stability during storage. This work also showed that the recycled PET is much less able to react with TPP in comparison with the virgin polymer. POLYM. ENG. SCI., 47:2155–2163, 2007. © 2007 Society of Plastics Engineers     

Crystallisation kinetics of novel branched poly(ethylene terephthalate): a small‐angle X‐ray scattering study

Three types of poly(ethylene terephthalate) (PET) were investigated: linear (unprocessed) bottle‐grade PET (intrinsic viscosity, IV ～ 0.82 dL g^?1); a branched PET produced from linear PET by reactive extrusion with 0.4% w/w pyromellitic dianhydride and pentaerythritol in 5:1 molar ratio (IV ～ 0.97 dL g^?1); and a control sample produced from the same linear PET by extrusion under the same conditions without the reactive agents (IV ～ 0.71 dL g^?1). A key finding is that the reactive extrusion process, presumably as a consequence of branching and branch distribution, significantly modifies the crystallisation kinetics and changes the final morphology. Using small‐angle X‐ray scattering (SAXS) and differential scanning calorimetry (DSC), the crystallisation kinetics of PET was monitored from the melt (270 °C) to a crystallisation temperature of either 205 or 210 °C. The IV of the branched PET was ～ 21% greater than that of the unprocessed PET, and the rate of melt crystallisation (from DSC measurements) was 510 s for the branched, 528 s for the control, and 640 s for the unprocessed PET. The lamellae spacings measured from the equilibrium SAXS patterns were ～160 ± 10 Å for the branched PET and ～180 ± 10 Å for the unprocessed PET. Such properties offer the potential for new applications requiring high‐melt‐strength PET. Copyright © 2006 Society of Chemical Industry     

Supercritical carbon dioxide (scCO2) dispersion of poly(ethylene terephthalate)/clay nanocomposites: Structural,mechanical, thermal,and barrier properties

Dispersed poly(ethylene terephthalate) (PET)/clay nanocomposites can lead to materials with superior barrier and mechanical properties. PET/clay nanocomposites were prepared by melting extrusion of PET with as‐received or supercritical carbon dioxide (scCO₂) predispersed Cloisite^® 30B (30B). The predispersion of 30B was assessed by WAXD, SEM, and TGA, and results indicated that scCO₂ processing could predisperse 30B and the surface modification of the clay was preserved after processing. The structure of PET/30B nanocomposites was investigated by WAXD and TEM confirming that PET has penetrated into the clays inter‐galleries and the predispersed clays lead to improved interfacial interaction and homogenous clay dispersion. Both tensile strength and Young's modulus were improved by 12.1% and 24.9% respectively, as incorporating of 3 wt % of scCO₂ processed clay. Differential scanning calorimetry (DSC) results indicated that clay particles served as nucleation agent could increase the crystallinity whereas had no impact on melting process. In addition, with the addition of 1 wt % of predispersed clay, a significant reduction of oxygen permeation (～33%) was achieved at 23 °C and the maximum reduction (44%) was achieved by adding 3 wt % processed clay. Moreover, we confirmed the effect of temperature on the permeation of PET/30B nanocomposites depended both on the Arrhenius behavior of the organic phases and tortuous path effects, where improved clay dispersion resulted in a higher effective activation energy. Moreover, the transparency of PET matrix was preserved for all nanocomposites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44779.     

Transfer of contaminant into solid food from a bottle made of bilayer polymers with a recycled and a virgin layer: Effect of the thicknesses of these polymer layers

The transfer of a contaminant into solid food from a bottle by radial diffusion is considered, when this bottle consists of two polymer layers, one being a recycled polymer, and the other, a virgin polymer. The virgin polymer layer located between the recycled polymer layer and the food plays the role of a functional barrier. The effect of the relative thicknesses of the recycled and the virgin layers on the contaminant transfer is especially studied. The results are expressed in terms of profiles of the concentration of a contaminant developed through the bottle and the food and of the kinetics of a contaminant transferred into the food. The contaminant concentration—time histories are also drawn at various places in the food. Dimensionless parameters are used to obtain results to use in various typical cases. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1291–1301, 1997     

Study of glycolysis of poly(ethylene terephthalate) recycled from postconsumer soft‐drink bottles. III. Further investigation

A modified glycolysis reaction of recycled poly(ethylene terephthalate) (PET) bottles by ethylene glycol (EG) was investigated. Influences of the glycolysis temperature, the glycolysis time, and the amount of catalysts (per kg of recycled PET) were illustrated in this study. The manganese acetate was used as a glycolysis catalyst in this study. Bis‐2‐hydroxyethyl terephthalate (BHET) and its dimer were predominately glycolysis products. It was found the optimum glycolysis temperature is 190°C. And the best glycolysis condition is 190°C of glycolysis temperature, 1.5 h of glycolysis time, and 0.025 moles of manganese acetate based on per kg of recycled PET. If the best glycolysis condition is conducted, the glycolysis conversion may be as high as 100%. For a given reaction time (1.0 h), the ln(% glycolysis conversion) is linear to 1/T (K^?1) and the activation energy (E) of glycolysis reaction is around 92.175 kJ/(g mole). The glycolysis conversion rate increases significantly with increasing the glycolysis temperature, the glycolysis time, or the amount of manganese acetate (glycolysis catalyst). Thermal analyses of glycolysis products were examined by a differential scanning calorimetry (DSC) and a thermogravimetric analysis (TGA). According to the definition of a 2³ factorial experimental design, the sequence of the main effects on the glycolysis conversion of the recycled PET, in ascending order, is the glycolysis time (0.18) < the amount of catalyst per kg of the recycled PET (0.34) < the glycolysis temperature (0.40). Meanwhile, the prediction equation of glycolysis conversion from the result of a 2³ factorial experimental design is ? = 0.259+0.20X₁+0.09X₂+0.17X₃+0.06X₁ X₂+0.145X₁X₃+0.05X₂X₃+0.035X₁X₂X₃. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2004–2010, 2003     

Processing and thermal properties of composites based on recycled PET,sisal fibers,and renewable plasticizers

This investigation focuses on the preparation of bio‐based composites from recycled poly (ethylene terephthalate) (PET) and sisal fibers (3 cm, 15 wt %), via thermopressing process. Plasticizers derived from renewable raw materials are used, namely, glycerol, tributyl citrate (TBC) and castor oil (CO), to decrease the melting point of the recycled PET (T_m ∼ 265°C), which is sufficiently high to initiate the thermal decomposition of the lignocellulosic fiber. All used materials are characterized by thermogravimetric analysis and differential scanning calorimetry, and the composites are also characterized via dynamic mechanical thermal analysis. The storage modulus (30°C) and the tan δ peak values of CT [PET/sisal/TBC] indicate that TBC also acts as a compatibilizing agent at the interface fiber/PET, as well as a plasticizer. To compare different processing methods, rheometry/thermopressing and compression molding are used to prepare the recycled PET/sisal/glycerol/CO composites. These two different methods of processing show no significant influence on the thermal properties of these composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40386.     

Toughening of recycled poly(ethylene terephthalate)/glass fiber blends with ethylene–butyl acrylate–glycidyl methacrylate copolymer and maleic anhydride grafted polyethylene–octene rubber

The aim of this study was to improve the toughness of recycled poly(ethylene terephthalate) (PET)/glass fiber (GF) blends through the addition of ethylene–butyl acrylate–glycidyl methacrylate copolymer (EBAGMA) and maleic anhydride grafted polyethylene–octene (POE‐g‐MAH) individually. The morphology and mechanical properties of the ternary blend were also examined in this study. EBAGMA was more effective in toughening recycled PET/GF blends than POE‐g‐MAH; this resulted from its better compatibility with PET and stronger fiber/matrix bonding, as indicated by scanning electron microscopy images. The PET/GF/EBAGMA ternary blend had improved impact strength and well‐balanced mechanical properties at a loading of 8 wt % EBAGMA. The addition of POE‐g‐MAH weakened the fiber/matrix bonding due to more POE‐g‐MAH coated on the GF, which led to weakened impact strength, tensile strength, and flexural modulus. According to dynamic rheometer testing, the use of both EBAGMA and POE‐g‐MAH remarkably increased the melt storage modulus and dynamic viscosity. Differential scanning calorimetry analysis showed that the addition of EBAGMA lowered the crystallization rate of the PET/GF blend, whereas POE‐g‐MAH increased it. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modification of poly(ethylene terephthalate) by combination of reactive extrusion and followed solid‐state polycondensation for melt foaming

A combination of reactive extrusion and followed solid‐state polycondensation (SSP) was applied to modify the virgin fiber grade poly(ethylene terephthalate) (v‐PET) and recycled bottle‐grade PET (r‐PET) for melt foaming. Pyromellitic dianhydride (PMDA) and triglycidyl isocyanurate (TGIC) were chosen as the modifiers for the reactive extrusion performed in a twin‐screw extruder. For comparison, commercially available chain extender ADR JONCRYL ADR‐4370‐S was also used. The characterizations of the intrinsic viscosity, i.e., [η], and rheological properties whose changes were correlated to the long chain branches introduced in the molecular structure were performed on the modified PET to evaluate their chain extension extent. The results revealed that the [η] of 1.37 dL/g was obtained for PMDA modified v‐PET while that of 1.15 dL/g for TGIC modified r‐PET. Such difference was attributed to the different reactivity of the two chain extenders with the two types of PET. Increases in shear viscosity and storage modulus, and the high pronounced shear thinning behavior were also observed in the modified PET. Finally, the foamability of the certain modified PET was verified by the batch melt foaming experiments. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42708.     

Recycling of carbon/epoxy composites

The recycling of carbon fibers from carbon/epoxy composites was attempted with a solvent method in nitric acid solutions. Gel permeation chromatography and gas chromatography/mass spectrometry showed that the epoxy resin could entirely decompose into low‐molecular‐weight compounds, and the main components of the dissoluble decomposed compounds were 2,4‐dinitrophenol and 2‐nitro‐4‐carboxylphenol. Electron probe microscopy showed no damage to the recycled carbon fibers. The single‐fiber tension strength loss of the recycled carbon fibers was 1.1% under the following conditions: a decomposition temperature of 90 °C, a nitric acid solution concentration of 8M, and a ratio of the sample weight to the nitric acid solution volume of 6 g:100 mL. Through orthogonal experimentation, the recycling conditions for the carbon/epoxy composites were examined. The best combination was a decomposition temperature of 90°C, a nitric acid solution concentration of 8M, and a ratio of the sample weight to the nitric acid solution volume of 4g:100 mL. This method could liquefy raw materials for rocket engine shells reinforced with carbon fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1912–1916, 2004     

瓶片再生高强PET短纤维成套生产设备和技术的研发

通过对回收瓶片原料特性的深入研究,结合生产企业的实际情况,编制了纺丝级再生PET瓶片的质量控制标准;在研究国内外短纤维先进设备的基础上,结合瓶片再生纺丝的工艺特点,对纺丝、后处理的关键设备进行了集成创新,开发了可以利用回收瓶片生产高强型涤纶短纤维的成套设备和工艺技术,达到国际先进水平。