GB581243A

GB581243A - An improved manufacture of lubricating compositions

Info

Publication number: GB581243A
Application number: GB2426/43A
Authority: GB
Original assignee: Standard Oil Development Co
Current assignee: Standard Oil Development Co
Priority date: 1941-12-30
Filing date: 1943-02-13
Publication date: 1946-10-07
Also published as: US2340036A

Abstract

The corrosive and staining properties of lubricating compositions comprising mineral lubricating oil and a small amount of an extreme pressure agent are inhibited by adding to the compositions a small amount of a metal or onium base salt of a condensation product obtained by heating an amino derivative of a phenol in which each amino group is attached to the benzene ring through an alkylene group and in which each amino group may contain alkyl, cycloalkyl or aryl groups by substitution. Metal salts mentioned are those of alkali or alkaline earth metals, magnesium, zinc, tin, cadmium or lead, while the onium base salts may be ammonium, alkyl ammonium, sulphonium, phosphonium or pyridonium, salts. The amino derivative of a phenol from which the condensation product is obtained may be represented by the general formula:- <FORM:0581243/III/1> where R is an alkylene linkage one or more of the hydrogen atoms of which may be substituted by alkyl groups, these alkyl groups being the same or different when more than one is present, n is a small whole number, X is hydrogen or one or more organic radicles especially alkyl, aryl or aralkyl radicles with or without substituent groups, and R1 is hydrogen or an alkyl, cycloalkyl or aryl radicle with or without substituent groups, for example another <FORM:0581243/III/2> residue, the two radicles R1 being the same or different. The preparation of suitable amino derivatives of phenols and the production of metal or onium base salts therefrom is described (see Group IV). The extreme pressure agents may be chlorine compounds, for instance chlorinated aliphatic or aromatic hydrocarbons such as chlorinated paraffin wax, kerosene, and aromatic, petroleum or coaltar solvents. These chlorine compounds may be employed in conjunction with sulphur compounds such as sulphurized fatty or mineral oil, organic sulphides, mercaptans, di- or polysulphides, xanthates, xanthogen sulphides or thiocarbonates. Alternatively extreme pressure agents containing both sulphur and halogen may be employed, for example the products obtained by treating unsaturated organic materials, such as cracked wax and fatty oils of the drying and semi-drying types, with a sulphur halide, or the products obtained by reacting an organic halogen compound with an inorganic sulphide, polysulphide, thiocarbonate or xanthate. It is stated that when complex alkylated phenols of high molecular weight in which several phenol radicles are linked by alkyl radicles in a single molecule, obtained by alkylation of phenols with chlorinated paraffin waxes or chlorinated petrolatums by the customary Friedel-Crafts type of synthesis, are converted to amino compounds of the type described above, the metal salts of the condensation products obtained by heating these amines reduce the pour point of the hydrocarbon lubricating oil if the latter is waxy, and also raise its viscosity index, improve its lubricating properties such as its film strength and improve its stability and resistance to oxidation. The lubricating compositions may be used in the preparation of greases and cutting oils, and other known addition agents or lubricants, such as fatty oils, fatty acid or naphthenic acid soaps, esters thickeners such as polyisobutylene, pour depressants, anti-oxidants, oil-soluble metal soaps, or dyes, may be incorporated. In an example, a lubricating composition comprises mineral lubricating oil, a sulphurized chlorinated kerosene prepared according to Specification 508,335 and (a) the barium, calcium or zinc salt of a condensation product or (b) a mixture of the barium salt of the condensation product and the condensation product itself, the condensation product in each case being prepared by reacting together paraformaldehyde, hydrochloric acid and para-isooctylphenol, treating the product with ammonia and heating. The Specification as open to inspection under Sect. 91 describes a lubricant composition comprising an active inorganic element in a form normally corrosive to metals but capable of substantially increasing the load carrying capacity of the lubricant and also a small proportion of an oil-soluble salt of an auto-condensation product of an hydroxy arylalkyl amine. This subject-matter does not appear in the Specification as accepted.ALSO:An ingredient of a lubricating composition (see Group III) is a metal or onium base salt of a condensation product obtained by heating an amino derivative of a phenol in which each amino group is attached to the benzene ring through an alkalylene group and in which each amino group may contain alkyl, cycloalkyl or aryl groups by substitution. Metal salts mentioned are those of alkali or alkaline earth metals, magnesium, zinc, tin, cadmium or lead, while the onium base salts may be ammonium, alkylammonium, sulphonium, phosphonium or pyridonium salts. The amino derivative of a phenol from which the condensation product is obtained may be represented by the general formula <FORM:0581243/IV/1> where R is an alkylene linkage one or more of the hydrogen atoms of which may be substituted by alkyl groups, these alkyl groups being the same or different when more than one is present, n is a small whole number, X is hydrogen or one or more organic radicles, especially alkyl, aryl or aralkyl radicles with or without substituent groups, and R1 is hydrogen or an alkyl, cycloalkyl or aryl radicle with or without substituent groups, for example another <FORM:0581243/IV/2> residue, the two radicles R1 being the same or different. Suitable amino derivatives of phenols may be prepared by reacting an alkyl phenol with formaldehyde and a hydrogen halide and treating the reaction product with ammonia or other strong nitrogen base such as diethylamine, diamylamine, piperidine, aniline, diphenylamine and ethanolamine. The amino derivatives of phenols thus produced may be highly complex substances since in the first stage of the reaction, say of p-iso-octyl phenol, formaldehyde and hydrogen chloride, not only is chlormethyl iso-octyl phenol produced, but also bis-chlormethyl iso-octyl phenol, chlormethyl bis-(iso-octyl hydroxy phenyl) methane and bis-(iso-octyl chlormethyl hydroxy phenyl) methane, while similarly, in the second stage of the reaction, amino derivatives of phenols containing more than one hydroxy benzyl group in the molecule may be produced. Phenols which may be used as starting materials for preparing the amino derivatives of phenols include phenols extracted from petroleum oil and the alkylation products of such phenols, other naturally occurring phenols such as cardanol, and alkyl phenols prepared by alkylation of phenols with olefins, including mixtures of olefins such as are obtained in cracked petroleum fractions, or by alkylation of phenols with alkyl halides, including chlorinated paraffin wax and chlorinated petrolatums. The chlorinated wax may contain dichlorides and polychlorides and may be used in alkylating phenols by the customary Friedel-Crafts type of synthesis to give complex alkylated phenols of high molecular weight in which several phenol radicles are linked by alkyl radicles in a single molecule. In alternative methods of preparing the amino derivative of a phenol, the aldehyde may be first reacted with the nitrogen base to form alkylolamines for reaction with the phenol, while the nitrogen base or the amino derivative of the phenol may be alkylated, for example with diethyl sulphate, an alkyl halide, an alcohol, a ketone or an olefine, or may be reduced with hydrogen. Or the hydrogen chloride and formaldehyde may first be reacted to form bis-chlormethyl ethers or an alphachlor alkyl ether and then reacted with a phenol and afterwards reacted with a nitrogen base, or the sodium salt of the phenol may be reacted with an aldehyde to give a dialkylol derivative and this, or the chloride obtained by reaction with hydrogen chloride, reacted with ammonia. Metal salts of the condensation products obtained by heating the amino derivatives of the phenols may be formed by reacting the condensation products with metallic bases or alcoholates. Other salts may be prepared from the alkali metal salt by double decomposition, for example, with a metal chloride or an onium base chloride. In examples, condensation products of amino derivatives of phenols are obtained by (1) reacting together p-iso-octyl phenol, paraformaldehyde and hydrochloric acid, treating the product with ammonia and then heating; (2) reacting the sodium salt of p-iso-octyl phenol with formalin, treating the product or the chloride of the product with ammonia and then heating; (3) heating together p-iso-octyl phenol, formaldehyde and ammonia; (4) reacting p-iso-octyl phenol with trioxy-methylene and ammonia and then heating; and (5) reacting iso-octyl phenol and ethoxy-methyl diethylamine to give diethylamino methyl iso-octyl phenol and then heating. Details are also given of the preparation of a metal salt by reacting the condensation product of example (1) with barium hydroxide. The Specification as open to inspection under Sect. 91 refers to oil-soluble salts of an auto-condensation product of an hydroxyarylalkyl amine and states that some of these may contain halogen. This subject-matter does not appear in the Specification as accepted.