Patent GB-633993-A (GB)
Title: Compounded oil
IPC: C10M159/18
Filed: 1948-01-12
Abstract: A hydrocarbon oil composition, which is resistant to deterioration under oxidizing conditions, contains (i) an oil-soluble alkyl or substituted alkyl thio- or seleno-ether and (ii) a salt of an organic-substituted inorganic acid.  The composition may be used as a lubricating oil, particularly in internal-combustion engines, a grease, particularly for the lubrication of bearings and gears, a heat transfer fluid, or an insulating oil, switch oil or transformer oil.  Additive (i) may be of the general formula R-X-R1, where R and R1 are the same or different alkyl radicles and X is sulphur or selenium. R and R1 may be either straight hydrocarbon chains or branched chains such as obtained from isobutylene polymers or interpolymers of butylene with isobutylene and other analogous olefin polymer derivatives.  Particularly mentioned are dialkyl thio- and seleno-ethers containing twelve or more carbon atoms in the molecule and at least one alkyl radicle of at least eight to ten carbon atoms. Alternatively, monothio- or dithio-dialkyl diethers of the general formula <FORM:0633993/III/1> may be employed, where R and R1 are alkyl radicles, R2 and R3 are hydrogen or alkyl radicles and n is a whole number.  Examples of these are monothioethane dialkyl diethers of formula R-S-C2H4-O-R1 and dithioethane dialkyl diethers of formula R-S-C2H4-S-R1. The corresponding diseleno-ethers may also be employed. Alternatively, sulphoxides such as those of formula <FORM:0633993/III/2> may be employed.  Additive (ii) may be a salt of an organic substituted acid of boron, carbon, silicon, arsenic, sulphur, phosphorus, germanium, tin, antimony, bismuth, chromium, molybdenum or manganese.  Specific types mentioned are salts of organic substituted carbonic acids, carbamic acids, germanols, germanonic acids, germanic acid anhydrides, stannonic acids, thiostannic acids, stibinous acids, stibonic acids and stibinic acids.  Salts of organic substituted acids of phosphorus mentioned are those derived from phosphonous, phosphinous, phosphonic, phosphinic or dithiophosphonous acids, monoesters of phosphorous, phosphoric, phosphonous, phosphonic or thiophosphonous acids, diesters of dithiophosphonous acids, or monothioesters or dithioesters of phosphoric acid.  Salts of organic substituted acids of sulphur mentioned are those derived from sulphonic, sulphinous or sulphonous acids or monoesters of sulphuric acid or of sulphinous acids.  The salts may be salts of such metals as calcium, strontium, barium, magnesium, zinc, cadmium, aluminium, zirconium, chromium, molybdenum, bismuth, tin, lead, iron, cobalt, nickel, manganese, vanadium, sodium, potassium, copper and silver.  Salts of basic salt-forming radicles such as ammonium or amine salts may alternatively be employed.  Additional ingredients which may be present in the hydrocarbon oil composition are blending agents, homogenisers, metal salts of organic acids, pour-point depressants, oiliness agents, extreme pressure addition agents, blooming agents, viscosity index improvers, thickening agents, metal soaps and stabilizing agents such as metal alcoholates.  Examples of metal salts of organic acids mentioned are metal salts of higher fatty acids, naphthenic acids, oil-soluble substituted phenols and carboxylic acids containing an aryl substituent.  Metal salts of higher fatty acids specified are the laurates, oleates, stearates and ricinoleates of aluminium, zinc, tin, magnesium, calcium, chromium and barium.  The naphthenates mentioned are salts of aluminium, zinc, magnesium, cobalt, cadmium, tin or manganese.  Metal phenates mentioned are those derived from phenols containing one or more alkyl, aryl, aralkyl or cyclic non-benzenoid hydrocarbon substituents, especially those phenates containing more than ten carbon atoms in the molecule, for example the aluminium, zinc, tin, magnesium, calcium, chromium or barium phenates derived from cetyl phenol. Examples of carboxylic acids containing an aryl substituent are phenyl stearic acid, naphthyl stearic acid, phenyl lauric acid, a -benzal stearic acid, a -benzal lauric acid and other acids of formula <FORM:0633993/III/3> , where R1 is an alkyl radicle and R2 is an aryl radicle.  Aluminium, zinc, tin, magnesium, calcium, chromium and barium salts of such aryl-substituted carboxylic acids may be employed.  Metal salts of polycarboxylic acids may also be present; examples of such acids are partial esters of oxalic, malonic, isosuccinic, alkyl tartronic, malic, oxyglutaric, hydroxy adipic, tartaric and citric acids as well as partial esters of other homologues of oxalic acid, alkyl homologues of isosuccinic acid and homologues of malic acid.  Aluminium, zinc, tin, magnesium, calcium, chromium and barium salts of such polycarboxylic acids are mentioned. The hydrocarbon oil of the composition may be mineral lubricating or synthetic hydrocarbon oil and the composition may take the form of a concentrate to be diluted with further oil before use.  In the examples, mineral oil compositions are described containing (1) potassium cetyl xanthate and dicetyl sulphide, (2) zinc N-pentamethylene dithiocarbamate and dicetyl sulphide, (3) calcium cetyl phenate, calcium cetyl phosphate and dicetyl sulphide, (4) calcium cetyl phosphate and cetyl ethyl thioether, dioctyl thioether, cetyl methyl thioether, dioctadecyl thioether, ethane dioctyl dithioether, dilauryl thioether, dilauryl selenide or dicetyl thioether and (5) calcium petroleum sulphonates and dicetyl sulphide. For comparison purposes, mineral oil compositions are described containing (a) calcium cetyl phenate and dicetyl sulphide or (b) one only of the following additives: potassium cetyl xanthate, dicetyl sulphide, cetyl ethyl thioether, calcium cetyl phosphate, dioctyl thioether, cetyl methyl thioether, dioctadecyl thioether, ethane dioctyl dithioether, dilauryl thioether, dilauryl selenide, calcium petroleum sulphonates and zinc N-pentamethylene dithiocarbamate.  The Specification as open to inspection under Sect. 91 refers to a hydrocarbon oil composition in which ingredient (i) is an ether of an element of Group VI (b) of the Periodic Table.  A list of suitable dialkyl thio- and seleno-ethers is given, some with two identical and some with two different alkyl radicles and it is stated that telluro ethers may be employed.  Dialkyl thioethers having substituents in the alkyl groups, including aryl and other non-aliphatic substituents, are also mentioned.  Dialkyl thioethers of this type include those of formula <FORM:0633993/III/4> derived from oleic acid esters, R, R1 and R2 being alkyl radicles.  As regards ingredient (ii), the formul  of the various known types of organic-substituted acids of boron, arsenic, carbon, silicon, phosphorus and sulphur, whose salts may be employed, are set out and many examples of suitable salts are given.  The organic substituent in the inorganic acid may be hydrocarbon and various alkyl, aryl, aralkyl, alkaryl and alicyclic radicles are specified or it may contain polar radicles, a number of which are listed.  Ingredient (ii) may also be a compound of the type (A) (X) (Z) (X1) (Rn), where A is a basic salt-forming substituent, X and X1 are selected from the group consisting of oxygen, sulphur, and selenium, Z is an acid-forming element selected from Groups III (A), IV, V (B) and VI (B) of the Periodic Table, R is an organic radicle and n is a whole number.  In the examples, mineral oil compositions contain (1) octyl benzyl dithiocarbonate or dibenzyl dithio-carbonate with or without dicetyl sulphide; (2) mono- or di-cetyl phosphoric acid with or without cetyl ethyl thioether. U.S.A. Specifications 2,228,658, 2,228,659, 2,252,984 and 2,252,985 are referred to. This subject-matter does not appear in the Specification as accepted.ALSO:The Specification as open to inspection under Sect. 91 refers to the preparation of salts of organic-substituted inorganic acids for use as additives to hydrocarbon oils.  Metals which may form the basic component of the salts are calcium, strontium, barium, magnesium, zinc, cadmium, aluminium, zirconium, chromium, molybdenum, bismuth, tin, lead, iron, cobalt, nickel, manganese, vanadium, sodium, potassium, copper and silver.  The salts, however, may be salts of basic-salt forming radicles, particularly ammonium and amine salts.  Amines whose salts may be employed are alkylamines such as triethylamine, alkylolamines such as triethanolamine, aromatic amines such as aniline, reduced nitrogen bases such as homologues of piperidine, and nitrogen bases obtained from petroleum.  In general, the metal salts may be prepared by direct neutralization of the acids or by reaction between the sodium salt and the desired metal ion.  Salts of organic-substituted boron acids.-The boron acids, such as boronic, boronic, thioboronic, mono-esters of mono-thio-organo-boric acids and of organo mono-thio-boric acids are set out in a very comprehensive list.  The preparation of partially esterified boric acid, and partially esterified boronic acids and also the preparation of alkyl and aryl boronic acids and boronic acids and of salts of the boronic acids are given in detail.  Salts of organic-substituted phosphorus acids.-Many of the phosphorus acids are mentioned including the partially esterified acids.  In particular the following preparations are mentioned: (1) An alcohol ROH is refluxed with P2O5 and diethyl ether to give REgHPO4 and EtPO3.  The former is hydrolysed to give RH2PO4 which is neutralized to give a salt; (2) an ester P(OR)3 is prepared by reacting an alcoholate of alcohol ROH with PCl3 and the ester is hydrolysed to give P(OR)2OH.  This is treated with alkali hydroxide to give a salt.  (3) Treatment of the ester P(OR)3 with alkyl halide yields an alkyl phosphonate ester which is hydrolysed and neutralized; (4) calcium salts are prepared by reacting a free acid of phosphorus with calcium carbide