Aromatic antioxidants

The pressurised dissolution/cooling procedure of Macko el al. [490], which uses a UV-transparent low-boiling point solvent, is fast and simple as no additional evaporation of the solvent, preconcentration or redissolution of the additive is necessary. Macko el al. [491] have given an extensive listing of HPLC analyses of aromatic antioxidants and UVAs which can be separated with n-heptane and n-hexane as the main component of the mobile phase. The method was also used for HPLC quantification of thioether antioxidants (Santonox R, Chimox 14 and Irganox PS 802) in MDPE [612],... 

CA 46, 1768 (1952). An easily combustible mixture suitable as fuel for incendiary bombs and grenades, flame throwers, etc. Consists of 7-14% volatile hydrocarbon fuel such as gasoline, and 93 to 86% of soap-type gelling agent, which is composed of Al oleate 50-75, Al stearate 25-50, to which is added about 1% of oxy-aromatic antioxident compound... 

Haider and Karlsson [15] developed a simple procedure for the determination of aromatic antioxidants and ultraviolet stabilizers in polyethylene using ultrasonic extraction. Chloroform was used for the isolation of Chi-massorb 944 from 150-pm-thick commerical low-density polyethylene and Irganox 1010 and Irgafos 168 from 25-pm medium-density polyethylene film. The recovery of the additives increased remarkably at higher temperatures and longer extraction times. At 60°C, quantitative recovery was achieved in 15, 45, and 60 minutes for Irgafos 168, Irganox 1010, and Chi-massorb 944, respectively. 

The LD-MS of Compound 8, which contains the Wingstay 300 antiozonant and an aromatic antioxidant, has characteristic peaks at m/z 268, 211, and 183 representative of the antiozonant and new peaks present at m/z 352, 288, 274, and 260. These latter three peaks are thought to represent the three molecular ions of the components of the antioxidant mixture in Goodyear s Wingstay 100, an aromatic amine antioxidant. 

Mdtois, P., Scholler, D., Bouquant, J. and Feigenbaum, A. Alternative test methods to control the compliance of food packaging materials with the European Union regulation the case of aromatic antioxidants and of bis(ethanolamine) antistatics based on H-NMR and UV-visible spectrophotometry. Food Additives and Contaminants, 1997, in press. 

Antioxidant and deactivation additives substituted phenols, dithiophosphates, dithiocarbamates, alkylated aromatic amines. 

The metal coordination complexes of both sahcylaldehyde phenyhiydrazone (91) and sahcylaldoxime provide antioxidant (92) protection and uv stabihty to polyolefins (see Antioxidants). In addition, the imines resulting from the reaction of sahcylaldehyde and aromatic amines, eg, p- am in oph en o1 or a-naphthylamine, can be used at very low levels as heat stabiLizers (qv) in polyolefins (93). 

Alkylation. Benzene and phenol feedstocks are readily alkylated under Friedel-Crafts conditions to prepare extensive families of alkylated aromatics. These materials generally are intermediates in the production of surfactants or detergents such as linear alkylbenzenesulfonate (LABS) and alkylphenolethoxylate (APE). Other uses include the production of antioxidants, plasticizers, and lube additives. 

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). 

Several stabilizers are useful in minimizing oxidative degradation during thermoplastic processing or in the bulk soHd. Phenothiazine, hindered phenohc antioxidants such as butylated hydroxytoluene, butylatedhydroxyanisole, and secondary aromatic amines in concentrations of 0.01—0.5% based on the weight of polymer, are effective. 

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). 

Although aminyl radicals are stable towards oxygen, they can oxidi2e other aromatic amines, phenols and thiols (10), and regenerate the diarylamine. Thus, mixtures of phenols and diarylamines frequendy show better antioxidant activity than either one alone. This is called synergism. 

Radical Scavengers Hydrogen-donating antioxidants (AH), such as hindered phenols and secondary aromatic amines, inhibit oxidation by competing with the organic substrate (RH) for peroxy radicals. This shortens the kinetic chain length of the propagation reactions. 

Stilbenequiaones such as (5) absorb visible light and cause some discoloration. However, upon oxidation phenolic antioxidants impart much less color than aromatic amine antioxidants and ate considered to be nondiscoloring and nonstaining. 

Aromatic Amines. Antioxidants derived from -phenylenediarnine and diphenylamine are highly effective peroxy radical scavengers. They are more effective than phenoHc antioxidants for the stabilization of easily oxidized organic materials, such as unsaturated elastomers. Because of their intense staining effect, derivatives of -phenylenediamine are used primarily for elastomers containing carbon black (qv). 

Radical Trapping. Figure 2 shows some of the reactions of aromatic amines that contribute to their activity as antioxidants and to their tendency to form highly colored polyconjugated systems. 

These compounds are used most frequentiy in combination with hindered phenols for a broad range of apphcations in mbber and plastics. They are also able to suppress color development caused by oxidation of the substrate and the phenoHc antioxidant. Unlike phenols and secondary aromatic amines, phosphoms-based stabilizers generally do not develop colored oxidation products. 

Antioxidants resistant to extraction by lubricants and gasoline are preferred for the stabili2ation of elastomers used in automotive appfications such as gaskets and tubing. Aromatic amine antioxidants, such as A/-phenyl-Ar-(p-toluenesulfonyl)-A-phenylenediamine [100-93-6] (37), with low solubifity in hydrocarbons, are extracted slowly from elastomers and are used for these appfications. 

Raw NBR containing 1.5% of the built-in antioxidant retained 92% of its original resistance to oxidation after exhaustive extraction with methanol. NBR containing a conventional aromatic amine antioxidant (octylated diphenyl amine) retained only 4% of its original oxidative stabiUty after similar extraction. 

It is also possible to graft an aromatic amine antioxidant bearing a sulfhydryl group on to the backbone of an elastomer. 

AGE-Gontaining Elastomers. The manufacturing process for ECH—AGE, ECH—EO—AGE, ECH—PO—AGE, and PO—AGE is similar to that described for the ECH and ECH—EO elastomers. Solution polymerization is carried out in aromatic solvents. Slurry systems have been reported for PO—AGE (39,40). When monomer reactivity ratios are compared, AGE (and PO) are approximately 1.5 times more reactive than ECH. Since ECH is slightly less reactive than PO and AGE and considerably less reactive than EO, background monomer concentration must be controlled in ECH—AGE, ECH—EO—AGE, and ECH—PO—AGE synthesis in order to obtain a uniform product of the desired monomer composition. This is not necessary for the PO—AGE elastomer, as a copolymer of the same composition as the monomer charge is produced. AGE content of all these polymers is fairly low, less than 10%. Methods of molecular weight control, antioxidant addition, and product work-up are similar to those used for the ECH polymers described. 

---