Synthesis and antioxidant activities in polyolefin of dendritic antioxidants with hindered phenolic groups and tertiary amine

Two novel primary antioxidants with dendritic structure and hindered phenolic groups were synthesized using 3‐(3,5‐diter‐butyl‐4‐hydroxyphenyl) propionic acid as raw material and dendritic poly(amidoamine) (PAMAM) as linker in chloroform. The antioxidant activities of the dendritic antioxidants were evaluated in polyolefin by melt flow index (MFI), yellowness index (Y.I.), and oxidation induction time (OIT). The dendritic antioxidants had excellent processing property and oxidation resistance behavior in polyolefin. At the same weighed amount of antioxidant, the MFI and Y.I. values of mulitiple‐extruded polyethylene (PE) stabilized with the dendritic antioxidants were smaller than those of the commercial antioxidants, as well as the OIT values of polyethylene (PE) stabilized with the dendritic antioxidants were larger. Applying to polypropylene, the antioxidant ability of the second‐generation dendritic antioxidant (G2.0 dendritic antioxidant) with larger molecular weight was superior to the commercial antioxidants and that of the first‐generation dendritic antioxidant (G1.0 dendritic antioxidant) was equal to the commercial antioxidants. The dendritic antioxidants can prevent polyolefin from breaking of macromolecular chain in processing and had stabilizing effect in polyolefin in service life by donating H‐atoms and electron to free radicals. The dendritic antioxidants combined with Irgafos 168 had improvement of antioxidant activities of the dendritic antioxidants in polyolefin. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of binary combined systems of antioxidants on the stabilization of peroxide‐cured low‐density polyethylene

The secondary antioxidants Irganox 168 and 242 and dilaurylthiodipropionate (didodecyl‐3,3′‐thiodipropionate) (DLTP) were chosen to be combined with the primary phenol antioxidants Irganox 300, 1010, 1035, and 1076, and the effects of the binary combined systems of antioxidants on the peroxide curing reaction and the long‐term stability of crosslinked low‐density polyethylene (XLPE) were studied through isothermal dynamic rheological and mechanical testing. The results show that the primary phenol antioxidants with lower melting points had better resistance to scorching and exhibited good synergistic effects with the secondary antioxidants. Irganox 168 had little resistance to scorching, whereas Irganox DLTP had moderate resistance, and Irganox 242 had the greatest resistance. Irganox 168 and DLTP guaranteed the mechanical properties well, whereas Irganox 242 reduced the tensile strength obviously. Irganox 300 and 1035 combined with secondary antioxidants performed poorly in long‐term thermal aging test, whereas Irganox 1076 in combination with secondary antioxidants displayed a moderate effect of aging resistance, and Irganox 1010 showed the best effect. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012     

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     

新型三元复配抗氧体系的设计及其在煤基均聚PP中的应用

设计了一系列由主抗氧剂、辅助抗氧剂、碳自由基捕捉剂组成的不同种类、不同配比抗氧剂体系,并将其用于煤基均聚聚丙烯（PP）的抗热氧老化性能改性中。其中以巴斯夫抗氧剂 Irganox®1010、Irgafos®168主辅抗氧剂质量比1∶1为对比基准,通过测试并对比添加新型三元复配抗氧体系改性 PP的氧化诱导时间（OIT）、黄色指数、熔体流动速率、力学性能等性能指标,从而开发煤基均聚PP的最佳耐热氧老化助剂配方。结果表明,当主抗氧剂为Irganox®1010、辅抗氧剂为 Irgafos®168质量比为 1∶1并与羟胺类抗氧剂 Revonox®420复合使用时,改性 PP的 OIT最长为 9. 8 min,黄色指数为 1. 3,熔体流动速率为 10. 7 g/10 min,综合性能最佳;当主抗氧剂为 Irganox®1010、辅抗氧剂为 Irgafos®168质量比为1∶2时,改性PP的抗黄变效果最好,由此设计并优化的抗氧剂体系及其配比对煤基均聚PP的耐长期热氧老化 改性配方设计具有重要的启示。     

Natural extracts as potential source of antioxidants to stabilize polyolefins

Several natural matrices were investigated as potential sources of antioxidants to be used as plastic additives. Extracts of four matrices obtained under the same experimental conditions were initially considered: green tea, black tea, Lippia citriodora and Hypericum androsaemum. Both, the antioxidant activity of the extracts and their content in flavanols and quercetin, were compared. The antioxidant activity was determined by DPPH analysis and the phenolic composition by high performance liquid chromatography (HPLC) using ultraviolet (UV) diode array and fluorescence (FL) detectors. Concentration of the flavanols reduced in the same way as their antioxidant activity starting with green tea, through black tea, Hypericum androsaemum, and Lippia citriodora. The performance of polypropylene samples stabilized with green tea extract, or its individual components catechin and epicatechin, was compared with samples stabilized with a mixture of the synthetic antioxidants Irganox 1076 and Irgafos 168. Each sample was extruded and consecutively reextruded up to four times. The melt flow index (MFI) and the oxidation induction time (OIT) of the samples were measured after each step. The obtained results showed the interest of this natural matrix as a potential source of antioxidants for plastics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Type of polypropylene material significantly influences the migration of antioxidants from polymer packaging to food simulants during microwave heating

Three different polypropylene materials, polypropylene homopolymer (PP), propylene‐ethylene random copolymer (PP‐R), and propylene‐ethylene copolymer (PP‐C) are commonly used in plastic containers designed for microwave heating of food. Migration of antioxidants, Irganox 1010 and Irgafos 168, from PP, PP‐R, and PP‐C during microwave heating in contact with different food simulants was investigated by utilizing microwave assisted extraction (MAE) and high performance liquid chromatography (HPLC). The polypropylene material significantly influenced the migration rate, which decreased in the order of increasing degree of crystallinity in the materials. PP homopolymer was the most migration resistant of the studied materials especially in contact with fatty food simulants. The use of isooctane as fatty food simulant resulted in rapid depletion of antioxidants, while migration to another fatty food simulant, 96% ethanol, was much more limited. Migration to aqueous and acidic food simulants was in most cases under the detection limits irrespective of microwaving time and temperature. The diffusion coefficients were similar to what have been found previously under similar conditions but without microwaves. The effect of swelling was shown by the large increase in the calculated diffusion coefficients when isooctane was used as food simulant instead of 96% ethanol. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of different additives and their mixtures on thermal stability of polyethylene synthesized using iron and titanocene hybrid catalysts

Traditionally, additives are introduced into a polymer matrix via extrusion process which consumes a high amount of energy. In this study, the use of different additives including antioxidants for the in‐reactor stabilization of polyethylene has been investigated in order to provide an energy saving system. Particular attention was dedicated to the efficiency of antioxidant influencing the catalysts activity and properties of polymers. The effect of the addition of Irganox 1330 and Irgafos 168 antioxidants and zinc stearate on the activities of metallocene, post‐metallocene, and their supported hybrid were studied. In addition, the effect of different additives on the thermal characteristics of the synthesized polymers and oxidative induction time (OIT) was evaluated. Our polymerization results exhibited that the factors such as chemical structure of antioxidant and its steric hindrance, type of catalysts, and their hybrid could affect the catalyst performance and OIT contents. The use of antioxidants mixture and hybrid of catalysts is a way that can increase oxidation resistance of polymers considerably. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45482.     

Structural effect of secondary antioxidants on mechanical properties and stabilization efficiency of polyamide 6/halloysite nanotube composites during heat ageing

Hindered phenol (Irganox 1010) was combined with two kinds of secondary antioxidants [i.e., tris(2,4‐di‐tert‐butylphenyl) phosphite (Irgafos168) and tris(nonylphenyl) phosphite (TNPP)] to form antioxidant mixtures, and their influences on mechanical properties and thermo‐oxidative degradation of polyamide 6 (PA6) and halloysite nanotube (HNT) filled composites were investigated. The results showed that the antioxidant combinations provided an improvement in the oxidative induction time, decomposition temperature (T_d), processability, and tensile properties of PA6. Irganox/TNPP (1:1) was found to exhibit the best thermal oxidative resistance. The study of heat ageing in the air oven at 130 °C showed that the stabilized composites with 5 wt % of HNT could retain 92% of strength without loss of modulus. The physical characteristics of antioxidants such as low volatility and possible interaction with filler in the composites played a crucial role in stabilizing efficiency during heat ageing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45360.     

Comparative study on natural antioxidant as an aging retardant for natural rubber vulcanizates

The research aim is mainly to investigate the effectiveness of natural antioxidant (NA) obtained from oil palm leaves (Elaeis guineensis) as an aging retardant in natural rubber (NR) vulcanizates. Comparison of NA with other commercial antioxidants, trimethyl quinoline (TMQ) and butylated hydroxy toluene (BHT), is investigated. The effect of natural and commercial antioxidants on NR vulcanizates was explored before and after aging. Aging test was carried out at 70°C for three different periods, 4, 7, and 14 days to determine aging property by performing the tensile and tear tests. NA shows lower tensile properties, crosslink density, tack strength but high tear strength compared to the commercial antioxidants, BHT and TMQ. However, upon aging NR vulcanizates with NA retains its properties equivalent to that of commercial antioxidants, BHT and TMQ. Thus, NA can be used as an aging retardant for short‐term protection in application requiring moderate tensile properties and can be used as alternative source for commercial antioxidant. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Antioxidation and mechanism of phosphites including the free phenolic hydroxyl group in polypropylene

Inhibiting the degradation of polypropylene (PP) in melt processing and usage is an important issue in the plastic industry. It is becoming more and more urgent to increase the antioxidation of phosphites alone while maintaining the water resistance. In this study, one phosphite antioxidant, named bis‐2,2′‐methyl‐4,6‐di‐tert‐butylphenyl phosphite (BM46TBPP), which contains a water‐resistant inner ring and a free phenolic hydroxyl group together, was synthesized. Then, antioxidation in PP was characterized with multiple extrusions and oxidation induction times (OITs). Finally, the hydrogen‐donating ability of this antioxidant was tested with 2,2‐diphenyl‐1‐picrylhydrazyl radical colorimetry to explain the antioxidation mechanism. The results show that the phosphite BM46TBPP displays better antioxidation than tris(2,4‐di‐tert‐butylphenyl) phosphite (Irgafos 168) in melt processing and OIT testing. Furthermore, the priority of this antioxidant was more obvious when it was used in the presence of oxygen, so the antioxidant even made the PP stabilized by it alone show a longer OIT value than the PP stabilized by the complex system including Irgafos 168 and 2,4‐di‐tert‐butylphenol because there was a free phenolic hydroxyl group in the BM46TBPP antioxidant molecule and the hydroxyl group made the antioxidant show intermolecular synergistic antioxidation through hydrogen donation to radicals. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44696.     

Antioxidant Activity of Seaweed Extracts: In Vitro Assays,Evaluation in 5 % Fish Oil‐in‐Water Emulsions and Characterization

In this study the antioxidant activity of absolute ethanol, 50 % ethanol and water extracts of two species of seaweeds, namely Fucus serratus and Polysiphonia fucoides, were evaluated both in in vitro assays and in 5 % fish oil‐in‐water (o/w) emulsions. The 50 % ethanolic extracts of P. fucoides showed higher antioxidant activity both in in vitro assays and in 5 % oil‐in‐water emulsion in the presence or absence of iron. In spite of the higher phenolic content and very good antioxidant activity in some of the in vitro assays, the absolute ethanol extracts of both the species showed a pro‐oxidative tendency in 5 % fish oil‐in‐water emulsion in the presence or absence of iron. In order to investigate the reason for the higher antioxidant activity of 50 % ethanolic extracts of P. fucoides, these extracts were further fractionated into polyphenol‐rich, protein‐rich, polysaccharide‐rich and low‐molecular‐weight fractions. These fractions were tested both in in vitro and in 5 % oil‐in‐water emulsions. The results of the present study showed that the main effect was due to the phenolic compounds. In conclusion, the 50 % ethanolic extracts of P. fucoides can be a potential source of natural antioxidants as these extracts have antioxidant activities similar to those of synthetic antioxidants such as BHT.     

环氧化苯乙烯-异戊二烯-苯乙烯嵌段共聚物的热氧老化研究

采用FI-IR研究了环氧化苯乙烯-异戊二烯-苯乙烯嵌段共聚物（ESIS）热氧老化前后的结构变化,并通过力学性能的测试考察了抗氧剂对ESIS抗热氧老化性能的影响。结果表明,ESIS在热氧老化过程中,环氧基和C=C双键减少,而由环氧基开环生成的羰基和羟基则显著增多。抗氧剂Irganox1010和Irgafos168的复合体系能够有效提高ESIS的抗热氧老化性能。     

Antioxidant and radical-scavenging activities of buckwheat seed components

The search for endogenous components in food ingredients exhibiting antioxidant activity has been intensified in order to eliminate synthetic antioxidants. Tocopherols are widely used as natural antioxidants, although their protective ability is not always sufficient. Buckwheat seed components were evaluated for antioxidant and free radical-scavenging activities using solvents of different polarities to isolate components from hulls and groats. Components extracted from buckwheat hulls were pro-oxidant in canola oil. Antioxidant activity of extracts from buckwheat groats increased when more polar solvents were used for extraction. The highest activity was observed for the methanolic extract. Radical-scavenging activity of buckwheat extracts was analyzed with DPPH (2,2-diphenyl-2-picryl-hydrazyl). This activity increased when the more polar solvents were used for extraction, with the highest activity observed for the methanolic extract. It was also observed that the radical scavenging effectiveness of extracts was concentration dependent. Analysis revealed the presence of tocopherols in the hexane extract, while methanolic extracts were rich in phenolic acids and flavonoids.     

The oxidative stability of biodiesel: Effects of FAME composition and antioxidant

A significant problem associated with the commercial acceptance of biodiesel is poor oxidative stability. This study investigated the effectiveness of individual and binary antioxidants to improve the oxidative stability of different types of biodiesel and distilled biodiesel. Results indicate that different types of biodiesel have different levels of oxidative stability, and that natural antioxidants and FAME composition play significant roles in determining oxidative stability. Synthetic antioxidants can enhance the oxidative stability of different types of biodiesel, and antioxidant activity increases as a function of its concentration. However, the effective activity level of antioxidant is dependent on biodiesel feedstock. Binary antioxidant formulations (TBHQ and PY) have a synergistic effect on oxidative stability of biodiesel. After long‐term storage at room temperature, the oxidative stability of untreated SBO‐based biodiesel significantly decreases as a function of time, while the addition of the antioxidant TBHQ can improve and maintain oxidative stability of biodiesel over an 18‐month period. However, the effectiveness of PY significantly decreases even after 2‐months.     

Stabilisation of edible oils with natural antioxidants

Natural antioxidants have recently gained increased interest because of the belief that natural food ingredients are better and safer than synthetic ones. The review presents the results on stabilisation of the main edible oils with different types of natural antioxidants. Sources of natural antioxidants are spices, herbs, teas, oils, seeds, cereals, cocoa shell, grains, fruits, vegetables, enzymes, proteins. Researchers concentrate on ascorbic acid, tocopherols and carotenoids as well as on plant extracts containing various individual antioxidants such as flavonoids (quercetin, kaemferol, myricetin), catechins or phenols (carnosol, rosmanol, rosamaridiphenol) and phenolic acids (carnosic acid, rosmarinic acid). Ascorbyl palmitate is regarded as a 'natural' antioxidant because it is hydrolysed in the body to ascorbic and palmitic acids. Among the herbs of the Lamiaceae family, rosemary has been more extensively studied and its extracts are the first marketed natural antioxidants. Oregano, which belongs to the same family, has gained the interest of many research groups as a potent antioxidant in lipid systems. The review concerns the following main topics: stabilisation of oil with individual natural antioxidants, interaction of antioxidants with synergists, stabilisation of oil with extracts or dry materials from different plant sources (e.g. herbs and spices), stabilisation at frying temperatures and in emulsions.     

Effect of evening primrose extracts on oxidative stability of sunflower and rapeseed oils

Antioxidative activities of evening primrose seed meal extracts in sunflower and rapeseed oils were compared with that of commercially used antioxidants, namely butylated hydroxytoluene (BHT), ascorbylpalmitate as well as Grindox‐118. The study was carried out under Schaal oven conditions at 60 °C and the weight gain was followed up by p‐anisidine value measurement following the oxidation. An Oxidograph apparatus monitored the oxidation of oils at 110 °C. Among the examined extracts, the ethyl acetate extract (0.2%), containing only 87 mg/g of total phenolics, exhibited a stronger antioxidant activity than BHT (0.01%) and effectively stabilised both oils. A strong antioxidative effect was also noted for the ethanol‐ethyl acetate extract (168 mg/g of total phenolics). The study showed that addition of ethyl acetate and ethanol‐ethyl acetate extracts could extend the sunflower and rapeseed oils shelf‐life by protecting oils from further decomposition that naturally occurs during thermal treatments.     

New natural antioxidants for protecting omega‐3 rich products

The long‐chain (LC) highly unsaturated omega‐3 fatty acids, EPA (eicosapentaenoic acid, 20:5) and DHA (docosahexaenoic acid, 22:6) are vital for a wide range of biological functions and are implicated in the prevention of numerous diseases. However, these fatty acids are highly susceptible to oxidation because of their unsaturated nature. Addition of antioxidants is one method to prevent lipid oxidation. As synthetic antioxidants may have carcinogenic effects at higher levels, the replacement of synthetic antioxidants with natural antioxidants is now in demand. We have isolated natural antioxidants from yoghurt, potato peel, fish protein hydrolysates and seaweed, which were able to protect highly unsaturated fish oil from oxidation. These antioxidant extracts may have potential for commercial exploitation.     

Effectiveness of antioxidants on lipid oxidation and lipid hydrolysis of cod liver oil

The capacity of the natural antioxidant from barley husks to retard oxidation of PUFA in cod liver oil (Gadus morhua) was investigated and compared to synthetic antioxidants. The results confirm the efficacy of a natural antioxidant derived from barley husks to slow down the progress of lipid hydrolysis and increase oxidative stability in cod liver oil. The rates of lipid hydrolysis and lipid oxidation were slowed down with increasing concentration of natural antioxidant used. Using 100 mg of the natural antioxidant was more effective than some synthetic antioxidants (BHA 200 mg and BHT 200 mg) against primary and secondary oxidation. The use of propyl gallate (PG) as an antioxidant (200 mg/kg in cod liver oil) was the most effective antioxidant employed in reducing the production of primary and delaying secondary oxidation products. The formation of free fatty acids (FFA) was significantly lower in samples with natural antioxidant (BE200 and BE100) than in the control samples. BHA and BHT were the most effective antioxidants employed to delay the lipid hydrolysis. Practical applications: The use of barley husks, which are residues of the brewing process, was optimized to obtain a crude antioxidant extract. Natural extracts of phenolic compounds with high antioxidant activity were obtained after prehydrolysis and delignification of barley husks. The raw extracts show more than two‐fold antioxidant capacity compared to BHT in terms of EC50. The results demonstrate the efficacy of a natural antioxidant derived from barley husks. The extract could be used in fatty foods (such as butter, oil, etc.) to prevent rancidity.     

Lipid characterization and antioxidant status of the seeds and meals of Camelina sativa and flax

Four different antioxidant activity assays including 2,2′‐azino‐bis(3‐ethylbenzothiazoline‐6‐sulfonic acid (ABTS), 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH), ferric reducing antioxidant power (FRAP) and oxygen radical absorption capacity (ORAC), and thiobarbituric acid reactive substances were performed on the methanolic and ethyl acetate extracts of Camelina seeds (CS), flaxseeds (FS), Camelina meal low fat (CMLF, 9.9% fat), Camelina meal high fat (CMHF, 24.6% fat), and flaxseed meal (FSM, 2.7% fat). In addition, the fatty acid profile, and phenolic, tocopherol, flavonoid, and glucosinolate contents of CS, FS, CMLF, CMHF, and FSM were studied. The major fatty acid was α‐linolenic acid (C18:3 n‐3) which was 33.2, 29.4, 30.2, 60.1, and 39.3% in CS, CMLF, CMHF, FS, and FSM, respectively. The methanolic extract of CMLF showed the highest values of ABTS, DPPH and FRAP and the highest content of phenolic compounds, flavonoids, and glucosinolates. The methanolic and ethylacetate extracts of CMHF showed the highest values for ORAC and α‐ and γ‐tocopherols. The ethylacetate extracts of seeds and meals of Camelina sativa and flax showed lower values for antioxidant activity, phenolic compounds, and flavonoids than the methanolic extracts. In general, Camelina and FS meals showed higher antioxidant activities, and phenolic and flavonoid contents than their respective seeds. Practical applications: Camelina sativa seeds (CS) and flaxseeds (FS) are rich sources of omega 3 oils. Their by‐products after oil extraction are an attractive source of proteins, lipids, fiber, and natural bioactive compounds such as antioxidants. These by‐products may be used to improve nutritional value and prevent lipid oxidation in feed or food systems.     

Antioxidant activity of macambo (Theobroma bicolor L.) extracts

Macambo is an edible fruit species from the Amazon Region with a high content of lipids (33%). Macambo samples were obtained from the Amazon Region, dried at 60 °C, milled (32 mesh sieve) and submitted to sequential extraction using ether, ethanol and water as solvents. The antioxidant activity of the ether, ethanol and aqueous extracts was 47%, 68% and 67%, respectively, and the antioxidant activity of the control butylated hydroxytoluene (BHT) was 64%. Three phenolic fractions were obtained with tetrahydrofuran: free phenolic acids, soluble and insoluble phenolic esters. The antioxidant activity of these fractions was 83%, 85% and 93% respectively, and the antioxidant activity of the control BHT was 64%. The phenolic acids were identified on the basis of relative retention times as compared with standards. The fractions obtained showed the presence of the following phenolic acids: salicylic, trans‐cinnamic, sinapinic, chlorogenic, protocatechinic, gallic, quinic, and p‐hydroxibenzoic acid. The presence of phenolic compounds in macambo fruit extracts may be responsible for its rather high antioxidant activity and the results obtained suggest that macambo extracts could be used as food antioxidants. Further studies are in progress to analyze the use of its extracts and phenolic fractions in edible oil shelf life.