Decrease in the performance of a phenolic antioxidant in preparation of inhibited polyethylene films by hot pressing

The effect exerted on the efficiency of the polymer inhibition by the conditions (pressure, treatment time, antioxidant concentration) of preparing films of polyethylene with Irganox 1010 phenolic antioxidant by hot pressing was studied. Blends of the antioxidant with the polymer were prepared by treatment of the binder particles with a solution of Irganox 1010 in acetone. After drying to remove the solvent, films were prepared from the dry blends by hot pressing. The films were subjected to oxidation in the molten state in air. Evolution of the characteristic IR absorption bands of the antioxidant and polymer was monitored. The inhibition efficiency was evaluated by the induction period of the film oxidation. Two interrelated processes occur concurrently in the course of hot pressing: sorption uptake of the antioxidant, resulting in its more uniform distribution in the bulk of the sample, and a decrease in the relative content of hydroxy groups, i.e., partial degradation of the inhibitor. The latter process can decrease the efficiency of the polymer inhibition. Therefore, in development of polymer compounds with enhanced oxidation resistance, it is necessary to optimize the process conditions, namely, the composition of the ingredients, the procedure for introducing the antioxidant, and the temperature and time of sample preparation.     

Chemiluminescence of polyethylene: The comparative antioxidant effectiveness of phenolic stabilizers in low‐density polyethylene

The thermal stabilizing efficiency of a range of phenolic antioxidants (Lowinox CA22, Lowinox WSP, Lowinox TBP6, Irganox 3114, Irganox 1330, and Cyanox 1790) was determined in polyethylene films with chemiluminescence and hydroperoxide analysis and compared with standard systems based on Irganox 1010 and 1076. Under both nitrogen and oxygen conditions, good correlations were obtained between the two methods, confirming the importance and role of the hydroperoxide functionality and its stability in the oxidative process. Chemiluminescence decay rates correlated well with the initial corresponding hydroperoxide contents, which were measures of the antioxidant efficiencies in the polymer. The antioxidant structure and volatility (melting points) were important parameters to consider in any such correlations and related very much to the methodology and conditions of analysis (i.e., the temperature and atmosphere). Some of the antioxidants themselves under nitrogen exhibited strong chemiluminescence, which appeared to be a legacy associated with their manufacturing history and the partial oxidation of their structures, which gave peroxide functionalities. This was more notable for the complex antioxidant structures. Under oxygen, higher levels of chemiluminescence were observed, and this was indicative of some level of oxidation associated with the antioxidant structures. With temperature‐ramping experiments, the chemiluminescence emission was significant and only observed at temperatures close to the melting points of the additives and/or polymer. Mobility was clearly an essential feature of this reaction emission because chemiluminescence was well observed when the molten state was reached. Under normal practical conditions, such levels of chemiluminescence, because of employed stabilizers, do not contribute significantly to the chemiluminescence emissions of stabilized polymer materials. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3312–3326, 2002     

Oxidation of polyethylene inhibited with a phenolic antioxidant under the conditions of contact with metallic zinc

The inhibiting power of a phenolic antioxidant upon introduction into polyethylene contacting with metallic zinc was examined. Conditions at which zinc enhances the inhibiting effect of the antioxidant were determined, and the mechanism responsible for this effect was suggested.     

Thermal degradation of polyethylene containing antioxidant and hydrophilic/hydrophobic silica

High-density polyethylene, its composites with hydrophilic/hydrophobic silica and the antioxidant BHT (butylated hydroxytoluene) were studied using the thermogravimetric analysis. It has been shown that filling with silica as well as introducing BHT into the unfilled polymer increases the thermal-oxidative stability of the polymer. Immobilized BHT is inactive and it suppresses the stabilizing effect of hydrophobic silica surface in the processes of thermal oxidation at the initial stage. However, being gradually released from the surface antioxidant prolongs the resistance of the polymer against oxidation.     

一种半受阻酚类抗氧剂中间体的合成及抗氧化性能研究

采用2-甲基-6-叔丁基苯酚和丙烯酸甲酯为原料,通过迈克尔加成反应合成半受阻酚类抗氧剂中间体β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸甲酯.条件优化实验确定该抗氧剂中间体的最佳合成工艺条件为:2-甲基-6-叔丁基苯酚与丙烯酸甲酯物质的量之比为1∶1.1,催化剂KOH与2-甲基-6-叔丁基苯酚的物质的量比为1∶10,丙烯酸甲酯滴加温度为90℃,丙烯酸甲酯滴加时间为30 min,反应温度为130℃,反应时间为5 h.在此条件下,半受阻酚类抗氧剂中间体β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸甲酯的收率大于70%,熔程41.6℃~44.0℃.IR和1H NMR证实所合成目标产物的化学结构与其理论结构相一致.DPPH法测定半受阻酚类抗氧剂中间体清除自由基的性能,并与全受阻酚类抗氧剂中间体β-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯进行对比.结果表明,由于邻位取代基的不对称效应,使得空间位阻较小的不对称抗氧剂中间体β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸甲酯清除DPPH·的活性高于邻位取代基空间位阻较大的对称抗氧剂中间体清除DPPH·的活性.     

Determination of antioxidant migration levels from low-density polyethylene films into food simulants

An analytical method for the determination of specific migration levels of phenolic antioxidants from low-density polyethylene (LDPE) into food simulant has been developed. The screening and response surface experimental designs to optimize the liquid-liquid extraction (LLE) of these antioxidants have been tested and the analyses have been carried out by reversed-phase high-performance liquid chromatography (HPLC) coupled with ultraviolet diode-array detector. The procedure developed has been applied to specific migration tests in different commercial LDPE films. The considered antioxidants have not been found upper the legislation limits although Ethanox 330 and Irgafos 168 have been found at trace level.     

Influence of chemically inert fillers on the efficiency of polyethylene inhibition by antioxidants

The influence of chemically inert dispersed fillers (Al₂O₃, SiO₂) on the efficiency of the polyethylene oxidation inhibition by commercial antioxidants (Irganox 1010, Neozon D) was studied. Introduction of chemically inert fillers into inhibited polymers alters the inhibitor distribution in the sample volume. The first fraction of the additive remains conventionally dissolved in the polymer (occurs in the dissolved state and in sorption sites), the second fraction is localized at the filler-polymer interface (separates out in the interfacial zone and accumulates in microcavities and voids of this zone), and the third fraction is adsorbed on the filler (forms an adsorption layer on the particle surface). As a result, the heat resistance of the filled polymer changes.     

Assessing the long-term performance of polyethylene stabilised with phenolic antioxidants exposed to water containing chlorine dioxide

The addition of chlorine dioxide disinfectant to tap water prevents the spread of infection but has a serious drawback in that it degrades materials used in piping, including pipes made of polyethylene. Efficient methods are required to assess the long-term performance of different combinations of antioxidants and polyethylene grades. We have previously presented a screening method which exposes solutions of phenolic antioxidants in squalane (a liquid, low molar mass analogue of polyethylene) to 70 °C water containing either chlorine dioxide or chlorine. This method assesses the stability of the antioxidants towards these aqueous chlorinated media by determining the oxidation induction time through differential scanning calorimetry. The same experimental set-up with two modifications was used in developing a new method. A 0.3 mm thick polyethylene tape replaced the squalane phase and the supply of fresh water containing chlorine dioxide (10 ppm at pH = 6.8) was continuous; this required minimum attention from the operator over the longer exposure time periods used. Tapes of medium-density polyethylene containing 0.1 wt.% of six different phenolic antioxidants were studied. A linear relationship was established between the times to reach antioxidant depletion in the polyethylene tape samples and the times in the squalane samples (with the same antioxidants at the same concentration). A linear relationship was also found between the initial antioxidant consumption rates in polyethylene and squalane. Infrared spectroscopy and scanning electron microscopy of drawn samples revealed the onset of surface oxidation and surface embrittlement in tape samples exposed beyond the time for antioxidant depletion.     

一类新型受阻酚抗氧剂的合成与表征

以3,5-丙酰氯和1.0代以氨为核的星型聚酰胺-胺为原料,通过缩合反应合成一类结构新颖的受阻酚抗氧剂,通过正交实验确定新型抗氧剂的最佳合成工艺条件为:n(3,5-丙酰氯):n(1.0代PAMAM)=5:1,溶剂三氯甲烷用量为40mL,反应时间为12 h,分段升温.此条件下,产品收率在65％以上,熔点为204.5℃～20...     

Surface modification of highly dispersed rubber fillers and pigments by titanate proadhesive and hydrophobic compounds

A method of modifying silicate and carbonate fillers with titanate coupling agents and proadhesive agents was worked out. The modification aimed at hydrophobization of filler surface by introduction to the surface of functional groups with chemical affinity to polymers. Optimum amounts of modifying substances and appropriate conditions for performing the modification process were established. The obtained fillers showed a high degree of hydrophobicity.The modified fillers were applied in rubber mixtures based on butadienestyrene or natural rubber, in polyurethanes, in PVC, and as pigments in oil dyes of high corossive resistance.     

Resolution of phenolic antioxidant mixtures employing a voltammetric bio-electronic tongue

This work reports the application of a Bio-Electronic Tongue (BioET) system made from an array of enzymatic biosensors in the analysis of polyphenols, focusing on major polyphenols found in wine. For this, the biosensor array was formed by a set of epoxy-graphite biosensors, bulk-modified with different redox enzymes (tyrosinase and laccase) and copper nanoparticles, aimed at the simultaneous determination of the different polyphenols. Departure information was the set of voltammograms generated with the biosensor array, selecting some characteristic features in order to reduce the data for the Artificial Neural Network (ANN). Finally, after the ANN model optimization, it was used for the resolution and quantification of each compound. Catechol, caffeic acid and catechin formed the three-analyte case study resolved in this work. Good prediction ability was attained, therefore allowing the separate quantification of the three phenols with predicted vs. expected slope better than 0.970 for the external test set (n = 10). Finally, BioET has been also tested with spiked wine samples with good recovery yields (values of 104%, 117% and 122% for catechol, caffeic acid and catechin, respectively).     

Determination of the antioxidant activity of phenolic compounds by coulometric detection

The combination of reversed-phase high-performance liquid chromatography with coulometric detection allows the detection of phenolic antioxidants in complex matrices like plant extracts with a high degree of sensitivity and selectivity. According to their voltammetric behaviour, phenolic acids and tocopherols show maximal detector response at low potentials (100-450 mV) while flavonoids show optimal response at two different potential values (one at 0-300 mV and one at 600-900 mV). The potential corresponding to maximal detector response (MDRP) of phenolic acids was shown to be inversely proportional to their antioxidant efficiency as determined in a lipidic model system under strong oxidizing conditions (110 degrees C, intensive oxygenation) or by the DPPH() test. However, such a relationship was not observed for flavonoids.     

Determination of antioxidant activity of phenolic antioxidants in a Fenton-type reaction system by chemiluminescence assay

The hydroxyl radical (*OH) has been implicated in various diseases, and it is therefore important to establish efficient methods to screen hydroxyl radical scavengers for antioxidant therapy. In this paper, a simple chemiluminescence assay was established to evaluate the *OH-scavenging capacity of phenolic compounds. This assay took advantage of the transient property of the Fenton reaction and the reaction between luminol and the hydroxyl radical, and effectively avoided the pro-oxidant action of some phenolic compounds. Fifteen phenolic compounds were assessed for their antioxidant activity in the Fenton reaction system, and even in the case of "pro-oxidants" that were excluded from the widely used deoxyribose (DR) assay. Since it overcomes the challenges that the traditional DR assay encounters, our method has promising applicative values: it is low-cost, time-saving, and reliable. It would also be more favorable than electron spin resonance (ESR) and radiolysis technology, which are known to be expensive and not commonly available to those specialized in free radical biology and medicine.     

Thermomechanical analysis of a polymer dispersed liquid crystal containing a thermoplastic elastomer

Bulk samples of polymer dispersed liquid crystals (PDLCs) containing polystyrene (PS) and a thermoelastic elastomer as polymer matrices, have been prepared by a thermally-induced phase separation method. Thermomechanical analysis measurements revealed that the PDLC containing the thermoplastic elastomer possessed rubber-like elasticity even in the mesomorphic temperature range of the LC while the PDLC based on PS showed plastic deformation during the measurement.     

Thermomechanical analysis of a polymer dispersed liquid crystal containing a thermoplastic elastomer

Bulk samples of polymer dispersed liquid crystals (PDLCs) containing polystyrene (PS) and a thermoelastic elastomer as polymer matrices, have been prepared by a thermally-induced phase separation method. Thermomechanical analysis measurements revealed that the PDLC containing the thermoplastic elastomer possessed rubber-like elasticity even in the mesomorphic temperature range of the LC while the PDLC based on PS showed plastic deformation during the measurement.     

Structure and dielectric properties of a thermoplastic blend containing dispersed metal

In the present work broadband dielectric relaxation spectroscopy measurements were employed to investigate the dielectric properties of polymer composites. A polyethylene/polyoxymethylene (PE/POM) thermoplastic blend was used as a matrix, while the inclusions were iron (Fe) particles. For comparison, the two pure polymers- PE and POM- were used as a matrix, too. In the PE/POM-Fe composites, the polymer matrix is two-phase and the filler particles are localized only in the POM phase, resulting in an ordered distribution of the dispersed filler particles within the blend. In PE-Fe and POM-Fe composites, the filler spatial distribution is random. The behaviour of all the composites studied is described in terms of the percolation theory. The PE/POM-Fe composites, based on the PE/POM blend, demonstrate different electrical behaviour compared to that of POM-Fe and PE-Fe systems. The percolation threshold value of the PE/POM-Fe composites was found much lower than that of the other two systems. The results were related to the microstructure of the composites. A schematic model for the morphology of the composites studied has been proposed. This model explains the peculiar behaviour of the PE/POM-Fe composites by taking into account the ordered distribution of the filler particles in a binary polymer matrix. Optical microscopy photographs confirm this model.     

The extractability of phenolic antioxidants into water and organic solvents from polyethylene pipe materials - Part I

Three commercial anti-oxidant systems have been studied regarding migration and chemical reaction in different polyethylene pipe materials during extraction in organic solvents and in hot water, 95-100 °C, under anaerobic and aerobic conditions. Materials made of crosslinked and non-crosslinked high density polyethylene, low density polyethylene and blends thereof were stabilized with different phenolic antioxidants: Irganox 1330, Irganox 1010, and Irganox 1076. The loss in stability with increasing extraction times was followed by oxidation induction time (OIT) measurements and by measuring the residual amounts of anti-oxidant by extraction. A gradual decrease in OIT and amount of anti-oxidant with increasing treatment time in water was observed for all samples. However, the behaviour of the three antioxidants was dissimilar. For materials containing Irganox 1330 three new species, possibly transformation products of the anti-oxidant, were found within the material. Larger decrease in anti-oxidant content in the polymer compared to corresponding loss in OIT indicates that the new species still have anti-oxidant capacity. On the other hand, corresponding transformation species could not be found within materials stabilized with Irganox 1010 or 1076. It is suggested that these antioxidants, which both contain ester groups, are hydrolyzed and that the new species migrate out into the surrounding water. Solvent extractions showed that crosslinking did not affect the extractability of the antioxidants. Actually, even with water as the extracting media, the network did not show any obstructive effect of the migration of the anti-oxidant. For peroxide crosslinked samples part of the anti-oxidant could not be extracted with solvent but we believe that grafting of antioxidants onto the polymer backbone is the most plausible explanation in this case. Additionally, we see a clear decrease in anti-oxidant loss with increasing crystallinity.     

Study on ablative properties and mechanisms of hydrogenated nitrile butadiene rubber (HNBR) composites containing different fillers

The ablative properties of hydrogenated nitrile butadiene rubber (HNBR) composites filled with fumed silica, organically modified montmorillonite (OMMT), or expanded graphite (EG) were examined. The HNBR/OMMT composite has the lowest linear ablation rate and the highest mass ablation rate and does not tend to be carbonized. On the other hand, the HNBR/EG composite has the highest linear ablation rate and the lowest mass ablation rate, and is prone to carbonization. The ablative properties of the HNBR/silica composite are between those of HNBR/OMMT and HNBR/EG. From the viewpoint of thermal shielding capability, the HNBR/OMMT has the best ablation resistance. Thermogravimetric analysis (TGA) on different HNBR composites indicated that the filler type has no significant effect on the thermal stability of the composites. To understand the ablation mechanisms, the char layers of different HNBR composites after ablation experiments were characterized by scanning electron microscopy (SEM), energy disperse X-ray spectroscopy (EDS), and wide-angle X-ray diffraction (WAXD). The results showed that the porosity in the char layers of the HNBR/OMMT composite was the highest and the corresponding structure was the loosest of the three composites. The montmorillonite (MMT) dispersed in HNBR experienced phase transition, melting and vaporization when exposed to the flame with the temperature over 2000 °C. Fumed silica only melted at such situation. On the other hand, the EG kept their original crystalline structures after the ablation test. Based on these results, the effect of the filler type on the ablation mechanisms of the HNBR composites was discussed.