Amine Antioxidants

Amine antioxidants Amine boranes Amine Guard... 

Antioxidants. Amine antioxidants are generally added to NBR adhesives. 

The isocyanate was allowed to react with antioxidant amines and alcohols to prepare sulfonyl azides containing either a urea or a carbamate linkage. 

Rubbers Accelerators Phenolic antioxidants Amine antioxidants [98, 100-115]... 

Antioxidants, amine and phenolic solvent extraction, gas chromatography 254... 

Nonox range of antioxidants (amine and phenolic types)... 

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

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. 

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). 

Oxidation of LLDPE starts at temperatures above 150°C. This reaction produces hydroxyl and carboxyl groups in polymer molecules as well as low molecular weight compounds such as water, aldehydes, ketones, and alcohols. Oxidation reactions can occur during LLDPE pelletization and processing to protect molten resins from oxygen attack during these operations, antioxidants (radical inhibitors) must be used. These antioxidants (qv) are added to LLDPE resins in concentrations of 0.1—0.5 wt %, and maybe naphthyl amines or phenylenediamines, substituted phenols, quinones, and alkyl phosphites (4), although inhibitors based on hindered phenols are preferred. 

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). 

Monofunctional, cyclohexylamine is used as a polyamide polymerization chain terminator to control polymer molecular weight. 3,3,5-Trimethylcyclohexylamines ate usehil fuel additives, corrosion inhibitors, and biocides (50). Dicyclohexylamine has direct uses as a solvent for cephalosporin antibiotic production, as a corrosion inhibitor, and as a fuel oil additive, in addition to serving as an organic intermediate. Cycloahphatic tertiary amines are used as urethane catalysts (72). Dimethylcyclohexylarnine (DMCHA) is marketed by Air Products as POLYCAT 8 for pour-in-place rigid insulating foam. Methyldicyclohexylamine is POLYCAT 12 used for flexible slabstock and molded foam. DM CHA is also sold as a fuel oil additive, which acts as an antioxidant. StericaHy hindered secondary cycloahphatic amines, specifically dicyclohexylamine, effectively catalyze polycarbonate polymerization (73). 

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. 

Antidegradants. Amine-type antioxidants (qv) or antiozonants (qv) such as the phenylenediamines (ppd) can significantly decrease scorch time. This is particulady tme in metal oxide curing of polychloroprene or in cases where the ppd had suffered premature degradation prior to cure. 

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. 

Stability. In order to have maximum effectiveness over long periods of time, an antioxidant should be stable upon exposure to heat, light, oxygen, water, etc. Many antioxidants, especially in the presence of an impurity when exposed to light and oxygen, are subject to oxidation reactions with the development of colored species. Alkylated diphenyl amines are least susceptible and the -phenylenediamine derivatives the most susceptible to direct oxidation. 

Antioxidant Types. Commercially available antioxidants may be divided into three general classes secondary amines, phenolics, and phosphites. 

In general, the amines are more active than the phenoHcs which are in turn more active than the phosphites. Amine antioxidants, however, often cause staining problems and are therefore used mainly in black stocks. The phenoHcs and phosphites are relatively nonstaining and are normally used ia light-colored mbbers. 

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. 

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