Chain phenolic antioxidants

Antioxidants markedly retard the rate of autoxidation throughout the useful life of the polymer. Chain-terminating antioxidants have a reactive —NH or —OH functional group and include compounds such as secondary aryl amines or hindered phenols. They function by transfer of hydrogen to free radicals, principally to peroxy radicals. Butylated hydroxytoluene is a widely used example. 

Materials that promote the decomposition of organic hydroperoxide to form stable products rather than chain-initiating free radicals are known as peroxide decomposers. Amongst the materials that function in this way may be included a number of mercaptans, sulphonic acids, zinc dialkylthiophosphate and zinc dimethyldithiocarbamate. There is also evidence that some of the phenol and aryl amine chain-breaking antioxidants may function in addition by this mechanism. In saturated hydrocarbon polymers diauryl thiodipropionate has achieved a preeminent position as a peroxide decomposer. 

Synergism can also arise from cooperative effects between mechanistically different classes of antioxidants, e.g., the chain breaking antioxidants and peroxide decomposers (heterosynergism) [42]. For example, the synergism between hindered phenols (CB—D) and phosphites or sulphides (PD) is particularly important in thermal oxidation (Table 2). Similarly, effective synergism is achieved between metal dithiolates (PD) and UV-ab-sorbers (e.g., UV 531), as well as between HALS and UV-absorbers, (Table 3). 

It has been proposed that the a-tocopheroxyl radical can be recycled back to tocopherol by ascorbate producing the ascorbyl radical (Packer etal., 1979 Scarpa et al., 1984). The location of a-tocopherol, with its phytyl tail in the membrane parallel to the fatty acyl chains of the phospholipids and its phenolic hydroxyl group at the memisrane-water interface near the polar headgroups of the phospholipid bilayer, enables ascorbate to donate hydrogen atoms to the tocopheroxyl radical. The suitability for ascorbate and tocopherol as chain-breaking antioxidants is exemplified (Buettner,... 

Synergism based on the mixture of a chain-breaking antioxidant (sterically hindered phenol) and a hydroperoxide decomposer (organic sulfides or phosphites). 

The chain decomposition of hydroperoxides was proved and studied for hydroperoxides produced by the oxidation of polyesters such as dicaprilate of diethylene glycol and tetra-valerate of erythritol [140], The retarding action of phenolic antioxidant on the decay of hydroperoxides was observed. The initial rate of hydroperoxide decomposition was found to depend on the hydroperoxide concentration in accordance with the kinetic equation typical for the induced chain decomposition. 

Intramolecular hydrogen bond is much stronger than the intermolecular hydrogen bond. The reactivity of such phenolic groups was studied by Pozdeeva et al. [51], Crown phenol A was synthesized, and the reactivity as chain terminating antioxidant in oxidized styrene (323 K) was studied. The chain terminating activity of this crown phenol A was compared with that of ionol. 

Polymer stabilization is another area in which the peroxide-decomposing and chain-breaking antioxidant properties of diorganotellurides has found utUity. Alone or in combination with phenol and phosphate antioxidants, electron-rich dialkylamino-substirnted diaryltellurides and alkylaryltellurides provided greatly enhanced polymer stability for a thermoplastic elastomer and for polypropylene. The effects were unique to the tellurides, with selenides not providing similar protective effects. ... 

Synergistic behavior by two antioxidants is not confined to compounds which inhibit by entirely different mechanisms—for example, two chain-breaking phenolic antioxidants may synergize one another. This homosynergism is caused by the suppression of the unfavorable chain propagation reactions of one phenoxy radical by a hydrogen atom transfer from the second phenol. 

The most useful and most thoroughly studied chain-breaking antioxidants are phenols and aromatic amines. These compounds can generally transfer a hydrogen atom to a peroxy radical. 

In recent years Emanuel, Neiman, and their respective schools have greatly contributed to the theory of antioxidant action by studying the phenomenon of the critical antioxidant concentration in terms of a degenerate branched chain reaction. The critical antioxidant concentration, a well-established feature of phenolic antioxidants, is one below which autoxidation is autocatalytic and above which it proceeds at a slow and steady rate. Since the theory allowed not only a satisfactory explanation of the critical antioxidant concentration itself but elucidation of many refinements, such as the greater than expected activity of multifunctional phenolic antioxidants (21), we wondered whether catalyst-inhibitor conversion could be fitted into its framework. If degenerate chain branching is assumed to be the result of... 

The most important chain transfer antioxidants are phenols and aromatic amines (B-81MI11502). They act by donating hydrogen to the peroxy radical with the formation of a stable free radical which does not take part in further chain reactions (equation 4). Two amine antioxidants, used in the rubber industry, are 6-dodecyl-l,2-dihydro-2,2,4-trimethylquinoline (1) and polymeric l,2-dihydro-2,2,4-trimethylquinoline (2). Because of its polymeric structure (2) is thermally stable, has low volatility and is non-blooming, i.e. it shows little tendency to migrate. 

An antioxidant ties up the peroxy radicals so that they are incapable of propagating the reaction chain or to decompose the hydroperoxides in such a manner that carbonyl groups and additional free radicals are not formed. The former, which are called chain-breaking antioxidants, free-radical scavengers, or inhibitors. are usually hindered phenols or amines. The latter, called peroxide decomposers, are generally sulfur compounds or... 

We will not go in depth into the subject of antioxidants (12), which is more a part of preformulation than a stress test, but the autoxidation mechanism does suggest that oxidation can be inhibited by peroxy radical scavengers (chain-breaking antioxidants) like phenol antioxidants, by heavy metal chelating agents, and by peroxide inactivating substances (preventive antioxidants). 

As a chemical class, nitrones have found heavy use in studies of reactions of superoxo and alkylperoxyl radicals.120,122,123Table 8.8 lists several examples. The rate constant for the reaction of STAZN with Me2C(CN)00CH2CH(00 )Ph was determined recently, k = 7.6 x 104 M 1 s-1 in chlorobenzene and 4.8 x 105M 1 s-1 in mixed chlorobenzene/methanol (95 5, v/v).122 This reaction is sufficiently fast for STAZN to be an efficient chain-breaking antioxidant with reactivity that is within one to two orders of magnitude of the phenolic antioxidants such as tocopherols. 

Primary antioxidants, also termed as chain-breaking antioxidants, interfere with the chain reaction in Scheme 2.1, by trapping radicals or labile hydrogen atom donors. These are exemplified by hindered phenols and alkylarylamines. Scheme 2.8 schematically demonstrates the scavenging activity of a typical hindered phenol. 

Burton, G.W., Ingold, K.U. 1981. Auto-oxidation of biological molecules. I. The antioxidant activity of vitamin E and related chain breaking phenolic antioxidants in vitro. J. Am. Chem. Soc. 103, 6472-6477. 

Primary antioxidants terminate free radical chains and function as electron donors. They include the phenolic antioxidants, butylated hydroxyanisole (BHA), butylated hydroxy-toluene (BHT), tertiary butyl hydroquinone (TBHQ), alkylgalates, usually propylgallate (PG), and natural and synthetic tocopherols and tocotrienols. 

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