Antioxidants requirements

It was very important to guarantee at least 1 min of on-line reaction time between ABTS and the antioxidants because fast antioxidants, such as trolox or ascorbic acid, reacted with ABTS almost immediately, but other antioxidants required more time. In our case, trolox and ascorbic acid presented TEAC values of 1.0... 

The in vitro oxidation products from tocopherol have been studied in detail although less is known about its in vivo metabolism. The oxidation of a-tocopherol is light-catalysed and accelerated by unsaturated fatty acids, metal salts and alkali. The structure of many of the products from chemical oxidation has been established (ref. 98). It is used in the form of the unnatural acetate in which form it may well be more chemically stable although the manifestation of antioxidancy requires the presence of the free phenol since its radical is stabilised by resonance and by steric effects with the participation of several contributory structures. It has been suggested, as mentioned earlier, that the activity of vitamins E and C are related synergistically and evidence from pulse radiolysis has supported this augmenting interaction on the effect of vitamin E (ref.130), depicted in the equation. 

First, the peroxyl radical abstracts a hydrogen atom from the phenolic antioxidant to yield a hydroperoxide and aroxyl radical that subsequently undergoes radical coupling to give peroxide products. The rate of oxidation of a lipid inhibited by a phenolic antioxidant requires consideration of the following reactions too ... 

Antioxidant and antiozonant types most commonly used are aromatic amines or phenolics, though others are also employed, and can be determined using a variety of techniques such as UV-visible spectrophotometry, FTIR, near-infrared spectroscopy, TEC, GC (if the material can be volatilized), supercritical fluid chromatography, and HPLC. Identification of unknown antioxidants requires a separation technique like chromatography followed by mass spectrometry, NMR, ETIR, X-ray crystallography, etc. Standardized TEC methods are given in ASTM D3156 and... 

Such antioxidants are used only for some special applications where a superior stabilizer system is needed, e.g., for long-term stabilization of cable and pipe cladding from LDPE or LLDPE. The amount of antioxidant required depends largely on the type of... 

Environmental Impact of Ambient Ozone. Ozone can be toxic to plants, animals, and fish. The lethal dose, LD q, for albino mice is 3.8 ppmv for a 4-h exposure (156) the 96-h LC q for striped bass, channel catfish, and rainbow trout is 80, 30, and 9.3 ppb, respectively. Small, natural, and anthropogenic atmospheric ozone concentrations can increase the weathering and aging of materials such as plastics, paint, textiles, and mbber. For example, mbber is degraded by reaction of ozone with carbon—carbon double bonds of the mbber polymer, requiring the addition of aromatic amines as ozone scavengers (see Antioxidants Antiozonants). An ozone decomposing polymer (noXon) has been developed that destroys ozone in air or water (157). 

Single-dose preparations intended for use in eye surgery do not contain excipient ingredients, in order to avoid tissue irritation. However, multiple-dose containers may require antioxidants (qv), antimicrobial preservatives, or buffers to maintain stabiHty and stefiHty. Such solutions are packaged in polyethylene flexible dropper units called droptainers or in glass dropper botdes. 

The tendency of aliphatic ethers toward oxidation requires the use of antioxidants such as hindered phenoHcs (eg, BHT), secondary aromatic amines, and phosphites. This is especially tme in polyether polyols used in making polyurethanes (PUR) because they may become discolored and the increase in acid number affects PUR production. The antioxidants also reduce oxidation during PUR production where the temperature could reach 230°C. A number of new antioxidant products and combinations have become available (115,120,124—139) (see Antioxidants). 

Selection of Proper Antidegradant. Because the various antioxidants function by different mechanisms, an antioxidant under one condition may become an oxidation promoter in a different condition. Therefore, an antioxidant should be carefully selected depending on service requirements. Most antioxidants are either amines, phenols, or phosphates. The following are some important properties in the selection of proper antidegradant that should be considered. 

It is difficult to find a single material that meets ah. requirements of a product. Consequently, quite often blends of antioxidants are used. Table 15 provides a summary of characteristics of commercially important antidegradants (39). 

Many antioxidants ia these classes are volatile to some extent at elevated temperatures and almost all antioxidants are readily extracted from their vulcanizates by the proper solvent. These disadvantages have become more pronounced as performance requirements for mbber products have been iacreased. Higher operating temperatures and the need for improved oxidation resistance under conditions of repeated extraction have accelerated the search for new techniques for polymer stabilization. Carpet backiag, seals, gaskets, and hose are some examples where high temperatures and/or solvent extraction can combine to deplete a mbber product of its antioxidant and thus lead to its oxidative deterioration faster (38,40). 

In general, one day of oven aging at 70°C corresponds to one year of natural or shelf aging (a minimum requirement for mbber products), whereas the oxygen and air bomb methods are more drastic. By varyiag the amounts and types or combiaations of antioxidants the relative effectiveness of these materials against normal oxygen deterioration can be determined. 

Antioxidants are used to retard the reaction of organic materials with atmospheric oxygen. Such reaction can cause degradation of the mechanical, aesthetic, and electrical properties of polymers loss of flavor and development of rancidity ia foods and an iacrease ia the viscosity, acidity, and formation of iasolubles ia lubricants. The need for antioxidants depends upon the chemical composition of the substrate and the conditions of exposure. Relatively high concentrations of antioxidants are used to stabilize polymers such as natural mbber and polyunsaturated oils. Saturated polymers have greater oxidative stabiUty and require relatively low concentrations of stabilizers. Specialized antioxidants which have been commercialized meet the needs of the iadustry by extending the useflil Hves of the many substrates produced under anticipated conditions of exposure. The sales of antioxidants ia the United States were approximately 730 million ia 1990 (1,2). 

Nearly all polymeric materials require the addition of antioxidants to retain physical properties and to ensure an adequate service life. The selection of an antioxidant or system of antioxidants is dependent upon the polymer and the anticipated end use. A product that will not be exposed to the elements for a long period of time such as polyethylene grocery bags does not need a long term stabilizer polyethylenes used to iasulate communication cable must be stabilized for many years of service. 

The stabili2ation of polyolefins used to insulate copper conductors requires the use of a long-term antioxidant plus a copper deactivator. Both A[,Ar-bis(3,5-di-/ A-butyl-4-hydroxycinnamoyl)hydra2ine (29) and 2,2 -oxamidobisethyl(3,5-di-/ A-butyl-4-hydroxycinnamate) (30) are bifimctional. They are persistent antioxidants that have built-in metal deactivators. Oxalyl bis(ben2yhdenehydra2ide) (28) is an effective copper deactivator when part of an additive package that includes an antioxidant. 

A sequence of tests has been devised to evaluate antioxidants for use in automotive crankcase lubricants. The Indiana Stirring Oxidation Test (ISOT) JISK2514 is an example of a laboratory screening test. The oil is stirred at 165.5°C in the presence of air. Copper and iron strips are used as metal catalysts. The development of sludge, viscosity, and acidity are deterrnined periodically. Failure time is determined when the development of acidity requires... 

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