Patent GB-788408-A (GB)
Title: Stabilized sulfur-containing substances
IPC: C08K5/42
Filed: 1955-07-05
Abstract: Sulphur-containing organic substances comprising sulphur-containing aliphatic hydrocarbons which normally evolve H2S are stabilized by mixing with an alkaline substance comprising a metal salt of a sulphonate or of a phenol or thiophenol sulphide or a mixture thereof and containing an excess of alkaline neutralizing agent, in proportions such that the weight of said alkaline substance X its neutralization number to a pH of 4 is at least equal to the weight of sulphur-containing substance X its saponification number, and heating the mixture at an elevated temperature for an extended period of time.  The neutralization number is the amount of acid, expressed as equivalent mgs. of KOH, required per 1000 g. of the alkaline substance, and the saponification number is the amount of KOH in mgs. to saponify 1000 g. of sulphur-containing substance.  The heating is preferably effected at 150-450 DEG  F. for 2-4 hours or more.  The organic substances treated include sulphurized and phospho-sulphurized paraffins, olefins, diolefins, acetylenes, olefin polymers, petroleum fractions or extracts, preferably olefins of at least C20 and at least 15 in a straight chain, and olefin polymers of M.W. 250-20,000.  Copolymers of olefins, especially iso or tert. olefins of less than C7, with diolefins or acetylenes are also specified, catalysts being of the Friedel-Crafts or peroxide type. The sulphurization is effected by heating with sulphur, sulphur chloride, phosphorus and sulphur, phosphorus sulphides or the like. High alkalinity metal sulphonates and phenol sulphides are prepared by using excess of basic metal compound for the neutralization and, in the case of phenate sulphides, in presence of carbon dioxide and steam.  The sulphonates may be derived from alkyl aromatics or lubricating oil base stocks, the preferred metals being Ba and Ca although mono- or polyvalent metals may be used.  Preferred phenol sulphides have the formula: <FORM:0788408/IV (b)/1> where R is at least one alkyl radical, the total carbon atoms therein attached to each nucleus being at least 5, X is O or S, and x is 1-4. Substituent atoms or groups, many being specified, may be present in the alkyl groups or on the nuclei. Many type formul  are given and specific examples include tert. octyl (or amyl) phenol sulphide, 2,4-di-tert. amyl phenol sulphide, 2 - hydroxy - 3,5 - di - tert. amyl - 41-diethylamino diphenyl sulphide, salicylic acid sulphide octyl ester, 2-stearoyl-4-amyl phenol sulphide, C16-C20 branched alkyl phenol sulphide, and bis (2,4-diamyl phenol) 4-amyl phenol dithioether.  High alkalinity complexes of the phenate sulphides and sulphonates may be prepared by treating blends in a solvent such as lubricating oil with excess of the basic metal compound.  The stabilized products are added to lubricating oils in amounts of 0.1-20 per cent or prepared as concentrates containing 20-50 per cent.  The base oils may be straight mineral oils or distillates, blends or residuals, refined or hydrogenated oils or synthetics such as oxo alcohol, glycol, complex, phosphoric or other esters, polymers of halohydrocarbons or olefins, carbonates, mercaptals, formals, polyglycols, polysiloxanes, hydrogenated coal or carbon monoxide products or blends of mineral with animal, vegetable or fish oils. Other additives may be dyes, pour depressors, soaps, organo-metallic compounds, anti-oxidants, V.I. improvers, resins, rubber, colloidal solids such as graphite or zinc oxide, solvents and higher alcohols including paraffinic, olefinic and cyclic or oils containing them. The products are also added to motor fuels, hydraulic and like fluids, greases, cutting and industrial oils generally.  The preparation is described of: "Product A" by heating a Panhandle residuum with P2S5 at 100 DEG  F. rising to 450 DEG  F. for 10 hrs.; "Product B" by heating solutions in diluent oil of calcium petroleum sulphonate and diisobutylphenol sulphide with water and mineral oil and adding Ba(OH)2.8H2O with final heating up to 302 DEG  F.; "Product C" in similar manner but using barium petroleum sulphonate and adding Ba(OH)2.5H2O; "Product D" by reacting diisobutylphenol sulphide with excess baryta in presence of CO2 and water; "Product E" by treating tert.-octylphenol sulphide and petroleum sulphonic acid with baryta in presence of water; "Product F" by heating the product obtained from polybutene and P2S5 with Product E and a diluent oil. In examples: (1) Product A is heated with barium diisobutylphenol sulphide containing excess barium at 310 DEG  F. for 4 hrs. and the product blended with a lub oil base stock containing polyisobutylene and polymethacrylate esters as improvers; (2)-(3) Products A and B are heated together at 280 DEG  F. for 6 hrs. and the products blended with a base oil; (4)-(6) phosphosulphurized polyolefins prepared from polyisobutylene and P2S5 are heated with Product D, C or B, and blended with a base oil; (7) Products A and B are blended in different proportions and at different temperatures; (8) a commercial high barium sulphonate is heated with phosphosulphurized polyisobutylene and blended with oil; (9) Products E and F are blended with oil.  Comparative lists show the improved stabilization compared with neutral salts or mixtures which are not heated together for an extended time.ALSO:Sulphur-containing organic substances comprising sulphur-containing aliphatic hydrocarbons which normally evolve H2 are stabilized by mixing with an alkaline substance comprising a metal salt of a sulphonate or of a phenol sulphide or thiophenol sulphide or a mixture thereof and containing an excess of alkaline neutralizing agent, in proportions such that the weight of said alkaline substance x its neutralization number to a pH of 4 is at least equal to the weight of sulphur-containing substance x its saponification number, and heating the mixture at an elevated temperature for an extended period of time.  The neutralization number is the amount of acid, expressed as equivalent mgs. of KOH, required per 1000 g. of the alkaline substance, and the saponification number is the amount of KOH in mgs. to saponify 1000 g. of sulphur-containing substance.  The heating is preferably effected at 150-450 DEG  F. for 2-4 hours, or more.  The organic substances treated include sulphurized and phospho-sulphurized paraffins, olefins, diolefins, acetylenes, olefin polymers, petroleum fractions or extracts, preferably olefins of at least C20 and at least 15 in a straight chain, and olefin polymers of M.W. 250-20,000. Copolymers of olefins, especially iso or tert. olefins of less than C7, with diolefins or acetylenes are also specified, catalysts being of the Friedal-Crafts or peroxide type.  The sulphurization is effected by heating with sulphur, sulphur chloride, phosphorus and sulphur, phosphorus sulphides or the like.  High alkalinity metal sulphonates and phenol sulphides are prepared by using excess of basic metal compound for the neutralization and, in the case of phenate sulphides, in presence of carbon dioxide and steam.  The sulphonates may be derived from alkyl aromatics or lubricating oil base stocks, the preferred metals being Ba and Ca although mono- or poly-valent metals may be used.  Preferred phenol sulphides have the formula <FORM:0788408/III/1> where R is at least on alkyl radical, the total carbon atoms therein attached to each nucleus being at least 5, X is O or S, and x is 1-4.  Substituent atoms or groups, many being specified, may be present in the alkyl groups or on the nuclei.  Many type formul  are given and specific examples include tert.-octyl (or amyl) phenol sulphide, 2,4-di-tert.-amyl phenol sulphide, 2 - hydroxy - 3,5 - di - tert. - amyl-41- diethylamino diphenyl sulphide, salicylic acid sulphide octyl ester, 2-stearoyl-4-amyl-phenol sulphide, C16-C20 brached alkyl phenol sulphide, and bis - (2,4 - diamyl phenol) - 4 - amyl phenol dithioether.  High alkalinity complexes of the phenate sulphides and sulphonates may be prepared by treating blends in a solvent such as lubricating oil with excess of the basic metal compound.  The stabilized products are added to lubricating oils in amounts of 0.1-20 per cent or prepared as concentrates containing 20-50 per cent.  The base oils may be straight mineral oils or distillates, blends or residuals, refined or hydrogenated oils or synthetics such as oxo alcohol, glycol, complex, phosphoric or other esters, polymers of halohydrocarbons or olefins, carbonates, mercaptals, formals, polyglycols, polysiloxanes, hydrogenated coal or carbon monoxide products or blends of mineral with animal, vegetable or fish oils. Other additives may be dyes, pour depressors, soaps, organo-metallic compounds, antioxidants, V.I. improvers, resins, rubber, colloidal solids such as graphite or zinc oxide, solvents, and higher alcohols including paraffinic, olefinic and cyclic or oils containing them. The preparation is described of: "Product A" by heating a Panhandle residuum with P2S5 at 100 DEG  F., rising to 450 DEG  F. for 10 hours; "Product B" by heating solutions in diluent oil of calcium petroleum sulphonate and diisobutylphenol sulphide with water and mineral oil and adding Ba(OH)28H2O with final heating up to 302 DEG F.; "Product C" in similar manner but using barium petroleum sulphonate and adding Ba(OH)25H2O; "Product D" by reacting diisobutylphenol sulphide with excess baryta in presence of CO2 and water; "Product E" by treating tert.-octylphenol sulphide and petroleum sulphonic acid with baryta in presence of water; "Product F" by heating the product obtained from polybutene and P2S5 with Product E and a diluent oil.  In examples: (1) Product A is heated with barium diisobutylphenol sulphide containing excess barium at 310 DEG  F. for 4 hours and the product blended with a mineral lubricating oil base stock containing polyisobutylene and polymethacrylate esters as improve