Degradation of low density polyethylene during extrusion. III. Volatile compounds in extruded films creating off‐flavor

This study was aimed at finding a correlation between the experienced off‐flavor in packaged foods and the presence of specific degradation products in PE packaging films. The possibility to trap degradation products by chemical reactions with scavengers, that is, zeolites and maleic anhydride grafted LLDPE, were investigated. This trapping would prevent the degradation products from migrating to the polymer film surface and further into food in contact with the film. This work concludes that off‐flavor in water packed in LDPE‐films depends on extrusion temperature and the content of oxidation products in the polymer film. At lower extrusion temperatures, reactive additives to the LDPE material could control the release of off‐flavor giving components. Adsorbents, such as zeolites, which are able to adsorb degradation products, are effective also at higher extrusion temperatures. The amount of oxidized degradation products in the films correlated well to the perceived off‐flavor in the packed water. The presence of aldehydes and ketones have a clear impact on the off‐flavor. The best correlation between off‐flavor and oxidized components were found for C₇? C₉ ketones, and aldehydes in the range of C₅ to C₈. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 847–858, 2005     

Degradation of low density polyethylene during extrusion. IV. Off‐flavor compounds in extruded films of stabilized LDPE

This study was aimed at finding a correlation between the experienced off‐flavor in packed foods and the presence of specific degradation products in LDPE packaging films. The possibility to trap degradation products by chemical reactions with scavengers, i.e., a zeolite additive or antioxidants, was investigated This would prevent degradation products from migrating to the polymer film surface and further into food in contact with the film. It was found that off‐flavor noted in water packed in LDPE films depended on extrusion temperature and exposure time for the melt to oxygen, that is, the parameters that influence the contents of oxidation products that are able to migrate from the polymer film. It was also found that adsorption of oxidative degradation products in a zeolite additive or protection of LDPE by using antioxidants could prevent off‐flavor in the packed product (water). However, the antioxidant should be selected with regard to extrusion temperature because thermal instability in the additive might jeopardize the intended effect. Multifunctional antioxidants seem to provide improved protection, the most effective one evaluated in this work being Irganox E201, i.e., vitamin E. Concentrations of oxidized degradation products are well correlated to the perceived off‐flavor in the packed water. The highest correlation between off‐flavor and oxidized components was found for ketones in the range of C₇ to C₉ and aldehydes in the range of C₆ to C₉. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 583–595, 2005     

Degradation of low density polyethylene during extrusion. I. Volatile compounds in smoke from extruded films

Many problems with odor and taste in food packaging can be traced to degradation of the packaging materials during processing. From this starting point, the degradation of polyethylene in a commercial extrusion coating process was studied by analyzing degradation products present in smoke sampled at the extruder die orifice. Two low‐density polyethylenes, A and B, with similar melt flow indexes and densities and obtained from different producers, were investigated. A third polymer, C, consisting of recycled material B, was also investigated. More than 40 aliphatic aldehydes and ketones, together with 14 different carboxylic acids, were identified in the smoke. The highest concentration was found for acetaldehyde, regardless of polymer and processing conditions. Increasing the extrusion temperatures in the range 280–325 °C increased the amounts of the oxidized products in the smoke. The extruded film thickness, 12 and 25 μm, influenced the concentrations of degradation products, with the thicker film giving higher amounts of product. The recycled polymer C generally gave lower concentrations of degradation products compared with the virgin polymer B. Differences in the product spectrum between the two virgin polymers may be related to differences in the manufacturing process. Many of the identified compounds have very characteristic taste and smell and are consequently of interest from an odor and taste point of view in food packaging applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1580–1586, 2002     

Degradation of polyethylene during extrusion. II. Degradation of low‐density polyethylene,linear low‐density polyethylene,and high‐density polyethylene in film extrusion

The degradation of different polyethylenes—low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and high‐density polyethylene (HDPE)—with and without antioxidants and at different oxygen concentrations in the polymer granulates, have been studied in extrusion coating processing. The degradation was followed by online rheometry, size exclusion chromatography, surface oxidation index measurements, and gas chromatography–mass spectrometry. The degradations start in the extruder where primary radicals are formed, which are subject to the auto‐oxidation when oxygen is present. In the extruder, crosslinking or chain scissions reactions are dominating at low and high melt temperatures, respectively, for LDPE, and chain scission is overall dominating for the more linear LLDPE and HDPE resins. Additives such as antioxidants react with primary radicals formed in the melt. Degradation taking place in the film between the die orifice, and the quenching point is mainly related to the exposure time to air oxygen. Melt temperatures above 280°C give a dominating surface oxidation, which increases with the exposure time to air between die orifice and quenching too. A number of degradation products were identified—for example, aldehydes and organic acids—which were present in homologous series. The total amount of aldehydes and acids for each number of chain carbon atoms were appeared in the order of C5>C4>C6>C7?C2 for LDPE, C5>C6>C4>C7?C2 for LLDPE, and C5>C6>C7>C4?C2 for HDPE. The total amounts of oxidized compounds presented in the films were related to the processing conditions. Polymer melts exposed to oxygen at the highest temperatures and longest times showed the presence dialdehydes, in addition to the aldehydes and acids. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1525–1537, 2004     

Extruded cylindrical strands: Mechanical properties correlated with the formation of biodegradable films through blown extrusion

The objective of this study was to determine the mechanical and viscoelastic properties of extruded cylindrical strands from biodegradable polymer blends and to verify the correlation of the blend properties with their capacity to form films in the blown extrusion process. The production of biodegradable films would only occur if the extruded strands showed adequate characteristics. The strands were produced by extrusion with blends containing starch, glycerol, and fatty acids (caproic, lauric, and stearic). These blends were compared with a standard formulation containing poly(butylene adipate‐co‐terephthalate) (PBAT), a biodegradable polymer. From the mechanical tension tests, the extruded strands containing fatty acids differed significantly from the standard one, it was not clear the possibility to establish a comparison between the mechanical properties of the extruded strands and the formation of films. The rheological tests indicated that the polymer blends presented the desired viscoelastic characteristics for the film formation by blown extrusion. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Cellulose supported copper nanoparticles as a versatile and efficient catalyst for the protodecarboxylation and oxidative decarboxylation of aromatic acids under microwave heating

Cellulose supported copper-nanoparticles is a versatile catalyst for the protodecarboxylation of aromatic and vinylic carboxylic acids to corresponding arenes and alkenes without using base or ligand is disclosed. The same nanoparticles catalyze the oxidative decarboxylation of phenylacetic acids to aromatic aldehydes in oxygen atmosphere and protodecarboxylation of phenylacetic acid to alkyl benzene in the absence of O₂ atmosphere. Decarboxylation reactions were performed in acetonitrile or water solvent under microwave heating. The conditions are mild enough to tolerate a wide range of different functional groups. The catalyst gives high yield and it is reusable up to four times, and hence green.     

Loss and transformation products of the aromatic antioxidants in MDPE film under long‐term exposure to biotic and abiotic conditions

The loss of a primary phenolic antioxidant Irganox 1010 and of a secondary phosphite antioxidant Irgafos 168 from a medium density polyethylene film (MDPE) was investigated after exposure of the film for 4 years to different environments such as aqueous media at pH5 and 7, open air, and compost, with an exposure of exposition of 25°C. An ultrasonic extraction technique using chloroform as extraction solvent was applied to recover the residual antioxidants from the polymeric matrix, and this was followed by High‐Performance Liquid Chromatography (HPLC) with acetonitrile as mobile phase and a quantitative analysis at a wavelength of 280 nm of the extracted antioxidants. The amount of antioxidant lost varied remarkably depending on the testing medium. The fastest loss of antioxidant was found on exposure to open air and sunlight while the slowest loss was observed in compost. Thermo‐analytical measurements were made to characterize the residual thermo‐oxidative stability of MDPE film in terms of oxidation temperature and oxidation induction time, to provide a greater insight into the underlying mechanisms of ageing in the different environments. Analysis by Gas chromatography–Mass Spectrometry (GC‐MS) revealed that degradation of the polymeric matrix resulted in the formation of hydrocarbons and oxygen‐containing compounds such as alcohols, carboxylic acids, aldehydes, and esters. The transformation products of the antioxidants formed as result of processing or exposure to the tested media were also identified. The transformation of the phenoxy radical of the Irganox 1010 produced the ester, acid, dealkylated cinnamate, and quinone products, whereas Irgafos 168 yielded oxidation products and the phenolic hydrolysis byproduct 2,4‐di‐tert‐butylphenol. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 974–988, 2002     

Structure‐Property Relationships of Extruded Starch, 2 Extrusion Products from Native Starch

The supermolecular structure and morphology of extruded flat films from several native starch materials of A‐ and B‐crystal type were investigated by wide‐angle X‐ray scattering and scanning electron microscopy. The degree of crystallinity and crystallite dimensions of both the different starting materials and the extruded films were determined and a scheme of the lattice transformations resulting from extrusion was established. The conditions of structure formation of the extruded starch films were varied in relation to plasticizer composition and extruder zone temperatures. The mechanical properties and biodegradability of the films were also measured. The extruded starches crystallized in the V_H polymorph with crystallinities between 33 and 41% and crystallite sizes of up to 35 nm. An increase in crystallite size was found for all starches (sometimes a doubling) with increasing extruder middle zone temperatures from 120 up to 210°C. For extruded potato and maize starches a steep rise in strength and modulus and a drop in elongation was observed above 190°C. Purified amylopectin from maize showed after extrusion the crystalline A‐type and small amounts of B polymorph with small crystallites (up to 3 nm) and the best mechanical performance with strengths and moduli of about 20 MPa and 1 500 MPa, respectively, for the present extrusion conditions. Native starch films that include 20 to 30% plasticizer biodegrade rapidly in 25 d consuming 90% of the oxygen needed for complete degradation, as analyzed by the Sapromat test.     

GC/MS characterization of effluents front the ozone bleaching of eucalypt kraft pulps

Concerns regarding the possible environmental effects of organochlorine by‐products from bleaching of pulp with chlorine‐based compounds have led to the pulp and paper industry developing new bleaching sequences. Ozone, oxygen and hydrogen peroxide are the main reagents in these Totally Chlorine Free (TCF) bleaching processes.

In this study, eucalypt kraft pulps from a variety of Australian wood sources were subjected to bleaching sequences comprising oxygen, ozone and hydrogen peroxide/alkali extraction stages. The aqueous liquid effluents from each stage were analyzed by GC/MS for aldehydes, ketones, alcohols, carboxylic acids and other by‐products. Pentafluorobenzyl oxime derivatives of the aldehydes and ketones were analyzed by electron impact GC/MS. The major carbonyl compounds detected were formaldehyde, glyoxal, dimethylglyoxal and acetone. An homologous series of n‐aldehydes corresponding to cleavage of ω‐3, 6, 9 and 12 unsaturated fatty acids also was detected. Aromatic aldehydes were identified in the oxygen stage and high consistency ozone stages, but not in any medium consistency ozone or post‐ozone bleach stages. In all stages a series of saturated alkyl carboxylic acids from formic to octacosanoic acid was detected. Formic and acetic acids were present in the highest yield. Only trace quantities of unsaturated fatty acids were detected. Details of these and other compounds detected are discussed.     

Crystallization of linear low density polyethylene under two-dimensional confinement in high barrier blend systems

Blends of linear low density polyethylene (LLDPE) and ethylene vinyl alcohol (EVOH) with different weight fractions are extruded to fabricate thin films. The extruded blend film morphology is investigated by atomic force microscopy (AFM). The extruded blend films have shown extended morphology along the extrusion direction (ED) and dispersed morphology along the transverse direction (TD). We report that due to this morphology, a two-dimensional (2-D) confined crystallization occurs. The EVOH has successfully confined the LLDPE from both film normal direction (ND) and transverse direction (TD) in this study. The confinement from ND results in an on-edge orientation of LLDPE, while the confinement from TD forces the on-edge oriented LLDPE crystals to further elongate and extend along the extrusion direction (ED). This specific crystal orientation is different from one-dimensional (1-D) confined crystallization observed in multilayered films. Both wide angle X-ray scattering (WAXS) and small angle X-ray scattering (SAXS) are utilized to investigate the crystal orientations of LLDPE in the extruded blend films. Moreover, due to the morphology, the extruded blend films have shown high oxygen barrier properties, which make this material valuable in packaging applications.     

Microporous membranes of polyoxymethylene from a melt‐extrusion process: (II) Effects of thermal annealing and stretching on porosity

A two‐part study utilizing polyoxymethylene (POM) was undertaken to investigate a three‐stage process (melt‐extrusion/annealing/uniaxial‐stretching) utilized to produce microporous films. In this report, the thermal annealing (second stage) and subsequent uniaxial‐stretching (third stage) results of selected POM films from two commercial resins, labeled D & F, are discussed. Specifically, the annealing and uniaxial stretching effects on film morphology, orientation, and other pertinent film properties are addressed. Additionally, sequential analysis was performed regarding the influence each stage had on the resulting microporosity. It was found that the melt‐extruded precursor morphology and orientation, as a consequence of the first stage extrusion parameters and resin characteristics, are crucial to controlling the membrane permeability. The annealing parameters were also deemed critical, where a temperature of 145°C applied for 20 min under no tension was the optimum annealing condition for producing a highly microporous film upon stretching. For the conditions studied, the stretching parameters that were found to be optimum for producing the desired characteristics in the final film were a cold temperature of 50°C and hot stretch temperature of 100°C. The optimum extension levels were concluded to be 90% for both the cold and hot stretch steps, and thus a total overall extension level of 180%. However, these results were only with respect to resin F films. Because the resin D melt‐extruded precursors possessed twisted lamellar morphologies and relatively low crystal orientation, their samples could not be produced into microporous films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1762–1780, 2002; DOI 10.1002/app.10587     

The flavor intensity of some carbonyl compounds important in oxidized fats

The flavor intensities of several methyl ketones, aldehydes, 2-enals, andtrans, trans-2,4-dienals were evaluated in 1% mineral oil in water emulsions against a series of standard emulsions of 2-heptanone. There was a linear relation between the logarithm of the concentrations of the carbonyls and the logarithm of the concentration of 2-heptanone giving an equal flavor intensity. Thresholds calculated from these linear relations were comparable to those reported in the literature. Mixtures of carbonyls similar to those found in oxidized soybean oil were evaluated, and their flavor intensities were similar to those predicted from adding the intensities of the individual carbonyls. The flavor intensity of these carbonyls could account for the flavor intensity of oxidized soybean oil.     

Biodegradation behavior of acid‐containing cellulose acetate film in soil

The biodegradation behavior of various cellulose acetate (CA; degree of substitution = 2.5) films that contain acids was examined by a laboratory soil burial test to clarify the effects of additives on the biodegradability of CA. The biodegradation rate of the CA films containing polyphosphoric acid, phosphoric acid, and p‐toluenesulfonic acid increased compared to that of the nonadditive CA film. CA films containing mandelic acid and maleic acid showed a small tendency to increase. Conversely, CA films containing adipic acid did not affect the biodegradability of CA. A similar experiment was carried out with a sterilization system. The acid‐containing CA film, which showed an accelerated biodegradation rate, was chemically deacetylated by contact with water in the environment and was consequently converted to a lower degree of acetyl group substitution matter that had higher biodegradability. An IR analysis suggested that this deacetylating ability of acids is correlated with the intensity of their interaction with the acetyl group of CA. In the biodegradation process, the contact efficiency of acids to CA was considerably lowered by the elution of internal acids with time. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 466–473, 2005     

红外光谱法研究降解聚丙烯薄膜的光降解性

本文用红外光谱法评价降解聚丙烯ＰＰ薄膜的光降解性。其研究结果表明，芳香酮类光敏剂与钴或铁络合物光敏剂协同使用，比前者单独使用，具有更好的自氧化或光氧化降解作用。在红外光谱１７１０ｃｍ－１和３４００ｃｍ－１附近出现明显多重缔合羰基和羟基宽峰，表明其氧化降解主要生成羧酸类和过氧化羰基类等含氧产物。     

Oxidation of Acetaldehyde and Propionaldehyde on a VOx/TiO2 Catalyst in the Presence of Water Vapor

The partial oxidation of acetaldehyde and propionaldehyde on a TiO₂ supported VO_x catalyst in the presence of water vapor was investigated at temperatures from 120 to 280 °C. Depending on the kind of aldehyde and reaction temperature, the selective oxidation to the appropriate carboxylic acid and an oxidative splitting to lower carboxylic acids took place. Acetaldehyde was oxidized to acetic acid with selectivities up to 82 % at ～ 200 °C whereas propionic acid was formed only with selectivities of about 20 % at ～ 140 °C in the oxidation of propionaldehyde. The oxidative cleavage of propionaldehyde led to the formation of more acetic acid than formic acid, which was in agreement with the higher formation of CO_x compared to that in the acetaldehyde oxidation. The presence of water and the increasing concentration of oxygen in the feed was found to enhance the selectivity towards the formation of C₁ to C₃ carboxylic acids by inhibiting the total oxidation of aldehydes and carboxylic acids.     

The weatherability of polypropylene monofilaments. Effects of fiber production conditions

From a comparison of the photo-and γ-irradiation-initiated oxidations of monofilaments and films, polypropylene oxidation rates and product ratios were found to be independent of sample morphology and orientation. Filament sensitivity to photo-oxidation was, however, drastically affected by extrusion and draw conditions, photosensitivity increasing with increasing draw speed and decreasing draw temperature. Draw effects were minimized by the exclusion of oxygen, indicating that free radicals produced by backbone cleavage during draw react with oxygen to give chromophoric oxidation products. The most important product detectable after drawing was probably the polypropylene hydroperoxide. A phenolic antioxidant reduced hydroperoxide formation, although sufficient hydroperoxide was still produced to accelerate photodegradation as compared with a similarly stabilized undrawn filament. Melt oxidation within the extruder was concluded to be much more important than thermal oxidation of the extruded filament as it cooled on the spinline.     

Auxetic polypropylene films

Auxetic materials are those exhibiting negative Poisson's ratio (ν) behavior. Polymeric auxetic extruded products in the form of cylinders and fibers have previously been reported. This article reports the successful production of auxetic polypropylene films (～0.15‐mm thick) using a melt extrusion process. Video extensometry and tensile testing techniques have been used to measure the in‐plane Poisson's ratios and Young's moduli of the auxetic film, both on an Instron tensile testing machine and a Deben microtensile testing machine. The film is elastically anisotropic with the Poisson's ratio and Young's modulus along the extrusion (x) direction being ν_xy = ?1.12 ± 0.06 and E_x = 0.34 ± 0.01GPa, respectively, while the Poisson's ratio and Young's modulus in the transverse (y) direction to the extrusion direction are ν_yx = ?0.77 ± 0.01 and E_y = 0.20 ± 0.01GPa, respectively. POLYM. ENG. SCI., 45:517–528, 2005. © 2005 Society of Plastics Engineers     

Microporous membranes of isotactic poly(4‐methyl‐1‐pentene) from a melt‐extrusion process. II. Effects of thermal annealing and stretching on porosity

A two‐part study utilizing isotactic poly(4‐methyl‐1‐pentene) (PMP) was undertaken to investigate a three‐stage process (melt‐extrusion/annealing/uniaxial stretching) (MEAUS) utilized to produce microporous films. In this report, the thermal‐annealing (second stage) and subsequent uniaxial‐stretching (third stage) results of selected PMP films from three resins, labeled A, B, and C, are discussed. From sequential analysis of the effect each stage had on the resulting microporosity, it was discovered that the melt‐extruded precursor morphology and orientation, as a consequence of the first‐stage extrusion parameters and resin characteristics, were crucial to controlling the membrane permeability. The annealing parameters were also critical, where a temperature of 205°C applied for 20 min under no tension was the optimum annealing condition for producing highly microporous PMP films upon stretching. For the conditions studied, the stretching parameters that were found to be the optimum for producing the desired characteristics in the final film were cold‐ and hot‐stretch temperatures of 70 and 180°C, respectively. The cold‐ and hot‐stretch extension levels concluded to be the best were a cold‐stretch extension of 80%, followed by hot stretching to 90%, and, thus, a total overall extension level of 170% for the processing window studied. However, these results were only with respect to resin A films, while resin B and C samples could not be produced into microporous films via the MEAUS process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1076–1100, 2002; DOI 10.1002/app.10395     

Catalytic degradation of oxygenates in Fischer–Tropsch aqueous phase effluents to fuel gas via hydrodeoxygenation over Ru/AC catalyst

BACKGROUND: Aqueous phase Fischer–Tropsch (FT) effluents co‐produced with hydrocarbons in the FT process contain various water‐soluble oxygenates, e.g. carboxylic acids, alcohols. Purification of the FT aqueous phase is important from the viewpoint of effective resource utilization and environmental stewardship. In this work, an aqueous‐phase hydrodeoxygenation process was investigated for the degradation of FT aqueous phases. RESULTS: The Ru/AC catalyst was determined to be the most active catalyst. The key parameters, i.e. temperature, pressure, weight hourly space velocity and Ru loading, were comprehensively optimized. Under optimal conditions, ca 98% of the oxygenates were converted to C₁～C₆ alkanes. The degraded water had no odour, a neutral pH, and as low as 1000 mg L^?1 chemical oxygen demand. The Ru/AC catalyst exhibited long‐term stability (1300 h) and no ruthenium leaching. A reaction pathway is proposed for this process in which the carboxylic acids are hydrogenated to alcohols via the formation of aldehydes. Alcohols and aldehydes are then converted to methane and alkanes of one carbon atom less than the substrate through C? C bond cleavage. CONCLUSIONS: This process is effective for treating FT aqueous phase effluent, and holds great promise for industrial applications due to its high efficiency, simplicity and stability. Copyright © 2011 Society of Chemical Industry     

Optimization of PE/Binder/PA extrusion blow‐molded films. I. Heat sealing ability improvement using PE/EVA blends

The optimization of three‐layer films (PE/binder/PA) manufactured by extrusion blow molding presents significant industrial challenges. The main issue consists in combining use properties (e.g., impermeability to water steam and oxygen, welding properties) with high mechanical, optical, and adhesion performances, while maintaining cost‐effectiveness. This article shows that the introduction of EVA in the PE layer improves the heat sealing ability and optical properties without degradation of the mechanical and adhesion performances. In the most favorable case, this modification leads to a 40% reduction of the heat sealing time, the other performances remaining either identical or higher. This leads to cost reduction of this manufacturing step while improving the flexibility of the process (wider process temperature window). The properties modifications observed can be explained by microstructure modifications (crystallinity, orientation, and molecular mobility). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 974–985, 2006