Antioxidant sulfur

High cis polybutadiene SBR 1500 Zinc oxide Stearic acid Flexamine antioxidant Sulfur N 242 black Santocure... 

Even before the nse of antioxidants (sulfur dioxide and ascorbic acid), the first recommendation for protecting wines against the adverse effects of chemical or microbiological oxidations was to limit their contact with air. Wines were stored in completely filled containers, sometimes equipped with a system permitting dilatation compensation. This recommendation cannot always be followed, if the availability of tanks of a satisfactory size is limited or wine is regularly taken from the same tank for several days. Tanks equipped with a sliding cover which always remains in contact with the surface of the wine were inffoduced, but the joints between the cover and the inner surface of the tank are rarely satisfactory and their effectiveness is questionable. 

More recendy, molecular molybdenum-sulfur complexes and clusters have been used as soluble precursors for M0S2 in the formulation of lubricating oils for a variety of appHcations (70). Presumably, the oil-soluble molybdenum—sulfur-containing precursors decompose under shear, pressure, or temperature stress at the wear surface to give beneficial coatings. In several cases it has been shown that the soluble precursors are trifunctional in that they not only display antifriction properties, but have antiwear and antioxidant characteristics as weU. In most cases, the ligands for the Mo are of the 1,1-dithiolate type, including dithiocarbamates, dithiophosphates, and xanthates (55,71). 

This addition is general, extending to nitrogen, oxygen, carbon, and sulfur nucleophiles. This reactivity of the quinone methide (23) is appHed in the synthesis of a variety of stabili2ers for plastics. The presence of two tert-huty groups ortho to the hydroxyl group, is the stmctural feature responsible for the antioxidant activity that these molecules exhibit (see Antioxidants). 

The bulk of 4-methylphenol is used in the production of phenoHc antioxidants. The alkylation of 4-methylphenol with isobutylene under acid catalysis yields 2-/ f2 -butyl-4-methylphenol [2409-55-4] and 2,6-di-/ f2 -butyl-4-methylphenol [128-37-0]. The former condenses with formaldehyde under acid catalysis to yield 2,2 -methylene bis(6-/ f2 -butyl-4-methylphenol) [119-47-1], which is widely used in the stabilization of natural and synthetic mbber (43). The reaction of 2-/ l -butyl-4-methylphenol with sulfur dichloride yields 2,2 -thiobis(6-/ l -butyl-4-methylphenol) [90-66-4]. 

Recipe, in parts by wt smoked sheets, 100.00 zinc oxide, 5.00 filler, as indicated nondiscoloring antioxidant, 1.00 MBTS, 1.00 TMTD, 0.10 sulfur, 2.75 stearic acid, 3.00. 

Dry basis natural mbber compound recipe, in part by wt high ammonia natural latex mbber concentrate, 100.0 potassium hydroxide, 0.5 Nacconal 90F (alkylarenesulfonate (AHied Chemical Co.)), 1.0 zinc oxide, 3.0 sulfur, 1.0 ZMBT, 1.0 zinc diethyldithiocarbamate (ZEDC) (trade names Ethazate (Uniroyal, Inc.), Ethyl Zimate (R. T. Vanderbilt), 0.3 antioxidant, as indicated. Wet-basis natural mbber compound recipe, in parts by wt natural latex (NC 356), 167.9 potassium hydroxide, 2.5 Nacconal 90F, 5.0 zinc oxide, 5.45 sulfur, 1.65 ZMBT, 2.0 ZEDC, 2.0 antioxidant, as indicated. AH films poured from freshly mixed compounds, dried overnight in place, then lifted and dried 1 h in air at 50°C before curing. 

The second class of grinding equipment is used to prepare dispersions. Typical of this class are baU and pebble mills, ultrasonic mills, and attrition mills. SoHds, eg, sulfur, antioxidants, accelerators, and zinc oxide, are generaUy ground on this equipment (see Size reduction). BaU mill action is assisted in some mills by a combination of dispersion circulation by an external pump and mechanical osciUation of an otherwise fixed nonrotary mill chamber. Where baU mill chambers are rotated it is necessary to experimentally estabHsh an optimum speed of rotation, the size and weight of the baU charge, and ensure the mills do not overheat during the grinding period. 

Protective Systems. As in the case of sulfur vulcani2ation, there have been many research workers in the field of natural mbber oxidation and its protection (39,40). The principal problem has always been to find an antioxidant that provides protection against flex-cracking, and yet does not stain. None has been found as of the mid-1990s, hence it is best to categori2e the various types according to their capabiUties. 

Rubber. The mbber industry consumes finely ground metallic selenium and Selenac (selenium diethyl dithiocarbamate, R. T. Vanderbilt). Both are used with natural mbber and styrene—butadiene mbber (SBR) to increase the rate of vulcanization and improve the aging and mechanical properties of sulfudess and low sulfur stocks. Selenac is also used as an accelerator in butyl mbber and as an activator for other types of accelerators, eg, thiazoles (see Rubber chemicals). Selenium compounds are useflil as antioxidants (qv), uv stabilizers, (qv), bonding agents, carbon black activators, and polymerization additives. Selenac improves the adhesion of polyester fibers to mbber. 

Antioxidants used in lubricants are also made by reaction of sulfur dichloride with phenols ... 

In kaolin (clay) processing, sulfur dioxide reduces colored impurities, eg, iron compounds. In the bromine industry, sulfur dioxide is used as an antioxidant in spent brine to be reinjected underground. In agriculture, especially in California, sulfur dioxide is used to increase water penetration and the avadabiHty of soil nutrients by virtue of its abiHty to acidulate saline—alkaH soils (327). It is also usefiil for cleaning ferric and manganese oxide deposits from tile drains (328). 

Additionally, organotin mercaptides can act as antioxidants, as they can sequester free-radical degradation mechanisms (48). The one drawback of mercaptide-based tin stabilizers is the discoloration of the sulfur after exposure to uv-radiation. Special precautions or formulations need to be developed for outdoor apphcations. 

Toluenesulfonic Acid. Toluene reacts readily with fuming sulfuric acid to yield toluene—sulfonic acid. By proper control of conditions, /)i7n7-toluenesulfonic acid is obtained. The primary use is for conversion, by fusion with NaOH, to i ra-cresol. The resulting high purity i7n -cresol is then alkylated with isobutylene to produce 2 (i-dii-tert-huty -para-cmso (BHT), which is used as an antioxidant in foods, gasoline, and mbber. Mixed cresols can be obtained by alkylation of phenol and by isolation from certain petroleum and coal-tar process streams. 

Divalent Sulfur Derivatives. A diaLkyl ester of thiodipropionic acid (16) is capable of decomposing at least 20 moles of hydroperoxide (17). Some of the reactions contributing to the antioxidant activity of these compounds are shown in Figure 3. 

Sulfur dioxide, sulfites, and metabisulfites have had extensive use as antimicrobial preservatives in the food industry. In pharmaceuticals they have had a dual role, acting as preservatives and antioxidants. The sulfa dmgs, or sulfonamides, the first effective chemotherapeutic agents to be employed... 

This combination of monomers is unique in that the two are very different chemically, and in thek character in a polymer. Polybutadiene homopolymer has a low glass-transition temperature, remaining mbbery as low as —85° C, and is a very nonpolar substance with Htde resistance to hydrocarbon fluids such as oil or gasoline. Polyacrylonitrile, on the other hand, has a glass temperature of about 110°C, and is very polar and resistant to hydrocarbon fluids (see Acrylonitrile polymers). As a result, copolymerization of the two monomers at different ratios provides a wide choice of combinations of properties. In addition to providing the mbbery nature to the copolymer, butadiene also provides residual unsaturation, both in the main chain in the case of 1,4, or in a side chain in the case of 1,2 polymerization. This residual unsaturation is useful as a cure site for vulcanization by sulfur or by peroxides, but is also a weak point for chemical attack, such as oxidation, especially at elevated temperatures. As a result, all commercial NBR products contain small amounts ( 0.5-2.5%) of antioxidant to protect the polymer during its manufacture, storage, and use. 

Isopropyl Ether. Isopropyl ether is manufactured by the dehydration of isopropyl alcohol with sulfuric acid. It is obtained in large quantities as a by-product in the manufacture of isopropyl alcohol from propylene by the sulfuric acid process, very similar to the production of ethyl ether from ethylene. Isopropyl ether is of moderate importance as an industrial solvent, since its boiling point Hes between that of ethyl ether and acetone. Isopropyl ether very readily forms hazardous peroxides and hydroperoxides, much more so than other ethers. However, this tendency can be controlled with commercial antioxidant additives. Therefore, it is also being promoted as another possible ether to be used in gasoline (33). 

The final possible mode of action for an antioxidant is as a peroxide decomposer. In the sequences that lead to photodegradation of a polymer the ready fragmentation of the hydroperoxide groups to free radicals is the important step. If this step is interfered with because the peroxide has undergone an alternative decomposition this major source of initiation is removed. The additives which act by decomposing hydroperoxide groups include compounds containing either divalent sulfur or trivalent phosphorus. The mechanism involves... 

All compositions contain EPDM, 100 phr zinc oxide, 5 phr stearic acid, 1 phr antioxidant, 1 phr 2-mercaptobenzothiazole (accelerator), 1.5 phr tetramethyl thiuram disulfide (accelerator), 1 phr and sulfur, 1.5 phr. 

It is of interest to examine the development of the analytical toolbox for rubber deformulation over the last two decades and the role of emerging technologies (Table 2.9). Bayer technology (1981) for the qualitative and quantitative analysis of rubbers and elastomers consisted of a multitechnique approach comprising extraction (Soxhlet, DIN 53 553), wet chemistry (colour reactions, photometry), electrochemistry (polarography, conductometry), various forms of chromatography (PC, GC, off-line PyGC, TLC), spectroscopy (UV, IR, off-line PylR), and microscopy (OM, SEM, TEM, fluorescence) [10]. Reported applications concerned the identification of plasticisers, fatty acids, stabilisers, antioxidants, vulcanisation accelerators, free/total/bound sulfur, minerals and CB. Monsanto (1983) used direct-probe MS for in situ quantitative analysis of additives and rubber and made use of 31P NMR [69]. 

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