Dithiophosphate

This is an analysis frequently conducted on oil lubricants. Generally, the additive is known and its concentration can be followed by direct comparison of the oil with additive and the base stock. For example, concentrations of a few ppm of dithiophosphates or phenols are obtained with an interferometer. However, additive oils today contain a large number of products their identification or their analysis by IR spectrometry most often requires preliminary separation, either by dialysis or by liquid phase chromatography. 

Anti-wear and extreme pressure additives phosphoric esters, dithiophosphates, sulfur-containing products such as fatty esters and sulfided terpenes or chlorinated products such as chlorinated paraffins. 

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

However, the most widely used materials are the zinc dialkyl-dithiophosphates that have an anti-wear effect in addition to their antioxidant power and, besides, offer an attractive cost/effectiveness ratio. 

For example, olefin sulfuri2ation products (Lubrizol, 1980), dithiophosphomolybdates (Mobil, 1980), or more simply the dithiophosphates of alcohol (Shell, 1980) whose anti-oxidant properties have been announced, are used in oil formulations for their anti-wear properties. 

When the operating temperature exceeds ca 93°C, the catalytic effects of metals become an important factor in promoting oil oxidation. Inhibitors that reduce this catalytic effect usually react with the surfaces of the metals to form protective coatings (see Metal surface treatments). Typical metal deactivators are the zinc dithiophosphates which also decompose hydroperoxides at temperatures above 93°C. Other metal deactivators include triazole and thiodiazole derivatives. Some copper salts intentionally put into lubricants counteract or reduce the catalytic effect of metals. 

Zinc dialkyl dithiophosphates are the primary oxidation inhibitors in combining these functions with antiwear properties in automotive oils and high pressure hydrauhc fluids. Their production volume is followed by aromatic amines, sulfurized olefins, and phenols (22). 

In steel-on-steel lubrication with a zinc dialkyl dithiophosphate additive, a complex surface paste appears to form first of zinc particles and iron dithiophosphate. The iron dithiophosphate then thermally degrades to a brown surface film of ZnS, ZnO, FeO, plus some iron and zinc... 

Xanthates and dithiophosphates dominate sulfide flotation usage, though several other collectors including more recently developed ones are gaining acceptance rapidly (43). As of this writing, this is an active area of research. Many of the sulfide collectors were first used ia the mbber iadustry as vulcanizers (16). Fatty acids, amines, and sulfonates dominate the nonsulfide flotation usage. The fatty acids are by-products from natural plant or animal fat sources (see Fats and fatty oils). Similarly petroleum sulfonates are by-products of the wood (qv) pulp (qv) iadustry, and amines are generally fatty amines derived from fatty acids. 

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). 

Dialkyl and diaryl dithiophosphoric acids are the bases of many high pressure lubricants, oil additives (see Lubrication and lubricants), and ore flotation chemicals (see Mineral recovery and processing). Organophosphoms insecticides such as Parathion are made by chlorination of the appropriate diaLkyl dithiophosphate and subsequent reaction of the intermediate dialkyl thiophosphoric chloride with sodium -nitrophenolate according to the following (see... 

Zinc dithiophosphates, which serve as antioxidants (qv) and antiwear agents in lubricants, are prepared by reaction of amyl alcohol and phosphoms pentasulfide followed by treatment with 2inc sulfate (43). 

Dithiophosphates. These compounds (13) are made by reaction of an alcohol with phosphoms pentasulfide, then neutralization of the dithiophosphoric acid with a metal oxide. Like xanthates, dithiophosphates contain no nitrogen and do not generate nitrosamines during vulcanization. Dithiophosphates find use as high temperature accelerators for the sulfur vulcanization of ethylene—propylene—diene (EPDM) terpolymers. 

The pH of the pulp to the flotation cells is carefliUy controlled by the addition of lime, which optimizes the action of all reagents and is used to depress pyrite. A frother, such as pine oil or a long-chain alcohol, is added to produce the froth, an important part of the flotation process. The ore minerals, coated with an oily collected layer, are hydrophobic and collect on the air bubbles the desired minerals float while the gangue sinks. Typical collectors are xanthates, dithiophosphates, or xanthate derivatives, whereas typical depressants are calcium or sodium cyanide [143-33-9] NaCN, andlime. 

Aetivators. These are used to make a mineral surface amenable to collector coating. Copper ion is used, for example, to activate sphalerite (ZnS), rendering the sphalerite surface capable of absorbing a xanthate or dithiophosphate collector. Sodium sulfide is used to coat oxidized copper and lead minerals so that they can be floated by a sulfide mineral collector. 

The fluorenyl-9-methyl group has been shown to be of particular value in studies of deoxynucleoside dithiophosphates. ... 

The zinc. salts of these acids are extensively used as additives to lubricating oils to improve their extreme-pressure properties. The compounds also act as antioxidants, corrosion inhibitors and detergents. Short-chain dialkyl dithiophosphates and their sodium and ammonium salts are used as flotation agents for zinc and lead sulfide ores. The methyl and ethyl derivatives (RO)2P(S)SH and (RO)2P(S)CI are of particular interest in the large-scale manufacture of pesticides such as parathion, malathion, dimethylparathion, etc. For example parathion. which first went into production as an insecticide in Germany in 1947. is made by the following reaction sequence ... 

Sulfur can replace 30-50% of the asphalt in the hlends used for road construction. Road surfaces made from asphalt-sulfur hlends have nearly double the strength of conventional pavement, and it has been claimed that such roads are more resistant to climatic conditions. The impregnation of concrete with molten sulfur is another potential large sulfur use. Concretes impregnated with sulfur have better tensile strength and corrosion resistance than conventional concretes. Sulfur is also used to produce phosphorous pentasulfide, a precursor for zinc dithiophosphates used as corrosion inhibitors. 

Photoelectron spectroscopy of metal dithiocarbamate, xanthate and dithiophosphate complexes. 

Tin, bis(diethyldithiocarbamato)diphenyl-angular parameters, 1,57 Tin, bis(diethyldithiocarbonato)diiodo-angular parameters, 1,57 Tin, bis(diethyl dithiophosphate)diphenyl-stereochemistry, 1,59 Tin, bis(diethyldithiophosphonium)diiodo-angular parameters, 1, 57 Tin, chlorotris(tropolone)-stereochemistry, 1, 82 Tin, cyclopentadienyl-, 3, 218 Tin, dibromobis(ethyldithiocarbonato)-angular parameters, 1, 57 Tin, dichlorobis(ethyldithiocarbonato)-angular parameters, 1, 57 Tin, dimethylbis(acetylacetone)-structure, 1, 58... 

Metal complexes of 1,1-dithiolates have been reviewed by Coucou-vanis (1) Eisenberg (2) presented a systematic, structural review of dithiolato chelates, and Stokolosa ct al. (3) reviewed dithiophosphate complexes in detail. Earlier reviews (4-3) covered less recent work in greater detail. Following initial work by Delepine (9), 1,1-dithiolato complexes were more intensively studied between 1930 and 1941 (10-16). There is, however, continuous interest in the synthesis, characterization, electronic structures, and bonding of these complexes. 

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