Patent GB-887334-A (GB)
Title: Improved sulfurized or phosphosulfurized detergent-inhibitor oil additive
IPC: C10M159/20
Filed: 1959-01-27
Abstract: A detergent material for use in oleaginous compositions, especially mineral lubricating oil compositions, is prepared by mixing a sulphurized or phosphosulphurized aliphatic hydrocarbon which normally evolves hydrogen sulphide with an alkaline substance comprising (a) a metal salt of an alkyl phenol or (b) a metal salt of a mixture of an alkyl phenol and a sulphonic acid or (c) a metal salt of a mixture of an alkyl phenol and an alkyl phenol sulphide, or mixture thereof, the said components (a), (b) and (c) containing an excess of alkaline neutralizing agent, in proportion such that the weight of the said alkaline substance multiplied by its alkaline neutralization number, as defined below to a pH of 4 is at least equal to the weight of sulphur-containing substance multiplied by its saponification number as defined below and heating the mixture at an elevated temperature for an extended period of time.  The alkaline neutralization number is defined as the amount of acid expressed as equivalent milligrams of potassium hydroxide which is required to react with one gram of the high alkalinity material to produce a pH of 4.  The saponification number is the milligrams of potassium hydroxide necessary to saponify one gram of the sulphurized or phosphosulphurized hydrocarbon.  Hydrocarbon materials specified for the preparation of sulphurized or phosphosulphurized hydrocarbons include heavy petroleum fractions and polybutenes.  Alkyl phenols for use in preparing the alkaline substance include phenols with from 1 to 30 carbon atoms in the alkyl radical, e.g. obtained by alkylating cresols or naphthols with olefins or by alkylating phenol with a mixture of normal and isobutenes together with other olefines obtained in the manufacture of butyl alcohol from petroleum refinery butenes.  Alkyl phenol sulphide for use in preparing the alkaline substance are produced by reacting alkyl phenols with sulphur dichloride to produce phenol monosulphides and with sulphur monochloride to produce alkyl phenol disulphides. Sulphonic acids employed in the preparation of the alkaline substance are produced by sulphoration of alkyl aromatic hydrocarbons, e.g. didodecyl benzene or by treating lubricating p  oil base stocks with concentrated or fuming sulphuric acid.  In examples: A detergent additive is obtained by heating a polybutene having a molecular weight above 1,100 with phosphorus pentasulphide; preparing an alkaline barium phenate by heating a phenol alkylated with tripropylene with barium hydroxide in the presence of mineral oil and completing the reaction whilst treating the reaction mixture with carbon dioxide and heating the phosphosulphurized hydrocarbon with the basic phenate in admixture with further mineral oil (I) and a further additive is prepared by adding a zinc dialkyl dithiophosphate, obtained by reacting phosphorous pentasulphide with a mixture of isopropanol and methyl isobutyl carbinol, neutralizing with zinc oxide and diluting with mineral oil, to the product obtained in Example (I), (II).  A list of conventional oil additives for use in addition to the detergents of the invention is furnished.ALSO:A process for reducing the evolution of hydrogen sulphide from a sulphurized or phosphosulphurized polyolefine, e.g. a polybutene polymer, which normally evolves hydrogen sulphide comprises mixing said sulphur containing substance with an alkaline substance comprising (a) a metal salt of an alkyl phenol or (b) a metal salt of a mixture of an alkyl phenol and a sulphonic acid or (c) a metal salt of a mixture of an alkyl phenol and an alkyl phenol sulphide, or a mixture thereof, the said components (a), (b) and (c) containing an excess of alkaline neutralizing agent, in proportion such that the weight of said alkaline substance multiplied by its alkaline neutralization number as defined below to a pH of 4 is at least equal to the weight of the sulphur-containing substance multiplied by its saponification number as defined below and heating the mixture at an elevated temperature for an extended period of time.  The alkaline neutralization number is defined as the amount of acid expressed as equivalent milligrams of potassium hydroxide which is required to react with one gram of the high alkalinity material to produce a pH of 4.  The saponification number is the milligrams of potassium hydroxide necessary to saponify one gram of the sulphurized or phosphosulphurized hydrocarbon.  Alkyl phenols for use in preparing the alkaline substance include phenols with from 1 to 30 carbon atoms in the alkyl radical, e.g. obtained by alkylating cresols or naphthols with olefins.  Alkyl phenol sulphides for use in preparing the alkaline substance are produced by reacting alkyl phenols with sulphur di- and mono-chlorides to produce respectively alkyl phenol mono- and disulphides.  Sulphonic acids employed in the preparation of the alkaline substance are produced by sulphonation of alkyl aromatic hydrocarbons, e.g. didodecyl benzene or lubricating oil base stocks.  In an example a detergent additive for use in lubricating oil is obtained by heating a polybutene having a molecular weight above 1,100 with phosphorus pentasulphide, preparing an alkaline barium phenate by heating a phenol alkylated with tripropylene with barium hydroxide whilst treating with carbon dioxide and heating the phosphosulphurized hydrocarbon with the basic phenate.ALSO:A process for reducing the evolution of hydrogen sulphide from a sulphurized or phosphosulphurized aliphatic hydrocarbon which normally evolves hydrogen sulphide comprises mixing said sulphur containing substance with an alkaline substance comprising (a) a metal salt of an alkyl phenol or (b) a metal salt of a mixture of an alkyl phenol and a sulphonic acid or (c) a metal salt of a mixture of an alkyl phenol and an alkyl phenol sulphide, or a mixture thereof, the said components (a), (b) and (c) containing an excess of alkaline neutralizing agent, in proportion such that the weight of the said alkaline substance multiplied by its neutralization number, as defined below, to a pH of 4 is at least equal to the weight of the sulphur-containing substance multiplied by its saponification number as defined below and heating the mixture at an elevated temperature for an extended period of time. The alkaline neutralization number is defined as the amount of acid expressed as equivalent milligrams of potassium hydroxide which is required to react with one gram of the high alkalinity material to produce a pH of 4.  The saponification number is the milligrams of potassium hydroxide necessary to saponify one gram of the sulphorized or phosphosulphurized hydrocarbon. Hydrocarbon materials specified for the preparation of sulphurized or phosphosulphurized hydrocarbons include heavy petroleum fractions and polybutenes.  Alkyl phenols for use in preparing the alkaline substance include phenols with from 1 to 30 carbon atoms in the alkyl radical, e.g. obtained by alkylating cresols or naphthols with olefines or by alkylating phenol with a mixture of normal and isobutenes together with other olefines obtained in the manufacture of butyl alcohol from petroleum refinery butenes.  Alkyl phenol sulphides for use in preparing the alkaline substance are produced by reacting alkyl phenols with sulphur dichloride to produce phenol monosulphides and with sulphur monochloride to produce alkyl phenol disulphides. Sulphonic acids employed in the preparation of the alkaline substance are produced by sulphonation of alkyl aromatic hydrocarbons, e.g. didodecyl benzene or by treating lubricating oil base stocks with concentrated or fuming sulphuric acid.  In an example a detergent additive for use in lubricating oil is obtained by heating a polybutene having a molecular weight above 1,100 with phosphorus pentosulphide; preparing an alkaline barium phenate by heating a phenol alkylated with tripropylene with barium hydroxide in the presence of mineral oil and completing the reaction whilst treating the reaction mixture with carbon dioxide, and heating the phosphosulphurized hydrocarbon with the basic phenate in admixture with further mineral oil.  In addition to their use in lubricating compositions (see Group III) the products of the invention can be employed in motor fuels, hydraulic fluids, torque converter fluids, cutting oils, flushing oils, turbine oils and transformer oils.