Patent GB-678151-A (GB)
Title: Improvements in lubricating oils
Filed: 1948-02-05
Abstract: Ethers are prepared by halogenating paraffin wax hydrocarbons having at least 18 carbon atoms in the molecule, separating at least one of the group consisting of "relatively pure" mono-, di- and so on halogenated hydrocarbons present in the halogenation product from the others and from unhalogenated hydrocarbons and replacing some or all of the halogen of the separated relatively pure halogenated hydrocarbon by reacting the same with a metal derivative of a compound of the type R1XH where R1 is an organic radical containing at least one cyclic nucleus and X is oxygen or sulphur.  The expression "relatively pure" means freedom from unhalogenated hydrocarbons and from less or more highly halogenated hydrocarbons though the separated fraction may be a mixture of, say, monochlorwaxes.  The initial wax materials may be chlorinated by passing chlorine through the melted wax until a weight of chlorine equivalent approximately to the desired derivative has been absorbed. The product or subsequently separated fraction may be stabilized by treatment with sodium sulphite, sodium bisulphite, sulphurous acid, potassium permanganate or sodium hypochlorite solutions. Bromination may be effected using bromine in presence of a halogen carrier such as the halides of antimony, phosphorus, iron or other metal.  The iodides or fluorides of the waxes may be made by direct halogenation or by preparing the chloro- or bromo-compounds and then before or after separation of the product into the desired relatively pure halo-waxes, converting the chloro- or bromo-compounds into the iodides or fluorides by reaction with a silver, lead, sodium or other iodide or fluoride.  The separation of the halogenated waxes into the relative pure halo-waxes is described with reference to the chloro-compounds.  The crude product may be filter-pressed at suitable temperature whereby the chlor waxes are liquid and the unhalogenated waxes are solids and separation occurs.  Sweating, selective solvent extraction at various temperatures or the use of diluents followed by chilling and settling or filtering may be used to separate mono-, di-and so on chlor-waxes from each other and also for separating unhalogenated wax.  Thus, the separated mixture of chlorinated waxes may be separated into the relatively pure fractions by crystallization from acetone, the monochlor waxes being the first to crystallize out.  An example illustrates this in relation to a C26 wax.  In place of acetone, there may be used methyl ethyl ketone, benzene, methylene chloride and other halogenated solvents; mixed solvents may also be used.  The relatively pure halowaxes are generally reacted with sodium or other alkali metal, alkaline-earth metal or heavy metal salts of the compounds R1XH at between 100 DEG and 300 DEG  C. to form the desired ethers. Examples of the compounds R1XH are phenol, p-nitrophenol, o-chlorphenol, triiodophenol, pentachlor phenol, nitro-chlorphenols, o-methyl amino phenol, picramic acid, phenol sulphonic acid and its salts, esters and its amides, vanillin, eugenol, thymol, mesitol, carvacrol, resorcinol, p-tert.-butyl phenol, cresols, xylenols, naphthols, hydroxy diphenyls, hydroquinone mono-methyl ether, amyl salicylate, p-hydroxy acetophenone, o-hydroxy benzo phenone, p-hydroxy benzaldehyde, o- or p-chlorobenzyl alcohol, cinnamyl alcohol, phenyl ethyl alcohol, di- and tri-phenyl carbinols, phenyl cyclohexanol, methyl cyclopentanol, m-hydroxy-azo-benzene, 8-hydroxy quinoline, hydroxy phenyl diphenyl phosphate, o-hydroxy phenyl diamyl phosphine, thiophenol, thionaphthols and 1-mercapto naphthyl disulphide. The reaction of halo-wax and compound R1XH may be so carried out as to leave residual halogen in the product or the latter may subsequently be halogenated or the reactant R1XH may be so selected as to contain halogen.  The ethers are used as lubricants or in lubricating compositions (see Group III).  Examples of the production of the ethers employ relatively pure mono- and di-chlor waxes obtained as above from white scale paraffin waxes of MPs. 142-145 DEG  F. and 158 DEG -162 DEG  F. respectively.  Thus, (1) monochlor wax is reacted with sodum phenate in toluene; (2) sodium o-cresolate is reacted as in (1); (3) phenol is tetra-alkylated by means of mono-chlor wax in presence of AlCl3 and the product in the form of its potassium salt is etherified as in (1); (4) the ether of (1) is alkylated by reaction with mono-chlor wax; (6) sodium benzyl alcoholate and (7) calcium o-chlor benzyl alcoholate are reacted with mono-chlor wax; (8) sodium cresolate is reacted with dichlor wax and (9) sodium cyclohexanolate is reacted with monochlor wax.  Reference is also made to ethers obtained from monochlor wax, and (12) sodium thiocresolate, and (14) sodium thionaphtholate, and (15) from the dichlor wax and sodium 8-hydroxy quinolate.  Reference is also made to a condensation product used in a composition (5) and obtained by reacting monochlor wax with naphthalene in methyl-cyclohexane in presence of AlCl3.  The Specification as open to inspection under Sect. 91, describes the production of ethers as above from paraffin hydrocarbons whose monochlor derivatives melt at lower temperatures than the hydrocarbons and metal derivatives of compounds R1XH where R1 is as above defined and X is an element from the right-hand side of Group VI of the Periodic Table, e.g. O, S, Se or Te.  Additional examples of reagents are cetyl chloride and octadecyl phenol, pentacosyl phenol, seleno-cresol and amyl cyclohexanol.  This subject-matter does not appear in the Specification as accepted.ALSO:Lubricating compositions having viscosity indices of over 90 comprise ethers prepared by halogenating paraffin wax hydrocarbons having at least 18 carbon atoms in the molecule, separating at least one of the group consisting of "relatively pure" mono-, di- and so on halogenated hydrocarbons present in the halogenation product from the others and from unhalogenated hydrocarbons and replacing some or all of the halogen of the separated relatively pure halogenated hydrocarbon by reacting the same with a metal derivative of a compound of the type R1XH in which R1 is an organic radical containing at least one cyclic nucleus and X is oxygen or sulphur (see Group IV(b)).  The expression "relatively pure" means freedom from unhalogenated hydrocarbons and from less or more highly halogenated hydrocarbons though the separated fraction may be a mixture of, say, mono-chlor waxes.  The ethers may contain halogen and thus chlorine, bromine, fluorine or iodine may be present in either portion of the ether molecule.  The ethers may be used as synthetic lubricating oils in conjunction with lubricant additives or they may be used in conjunction with mineral oils of lubricating viscosities. Examples of compounds R1XH used to provide the ethers are phenol, p-nitro-phenol, o-chlor phenol, tri-iodophenol, pentachlorphenol, nitro-chlorphenols, o-methyl amino phenol, picramic acid, phenol sulphonic acid and its salts, esters and amides, vanillin, eugenol, thymol, mesitol, carvacrol, resorcinol, p-tert-butyl phenol, cresols, xylenols, naphthols, hydroxy diphenyls, hydroquinone-monomethyl ether. amyl salicylate, p-hydroxyacetophenone, o-hydroxybenzo-phenone, p-hydroxybenzaldehyde, o- or p-chlorobenzyl alcohol, cinnamyl alcohol, phenyl ethyl alcohol, di- and triphenyl carbinols, phenyl cyclohexanol methyl cyclopentanol, m-hydroxy azo benzene, 8-hydroxy quinoline, hydroxy-phenyl diphenyl phosphate, o-hydroxy phenyl diamyl phosphine, thiophenol, thionaphthols and 1-mercapto naphthyl disulphide.  The finished lubricant may be so prepared as to contain from 0.2-20.0 per cent by weight of one or more halogen, sulphur, nitrogen or phosphorus atoms.  Lubricating compositions described in examples comprise (5) an ether from sodium o-cresolate and mono-chlorwax, Mid-Continent neutral oil, bright stock and a naphthalene - chlorwax condensation product; (10) the ether of (5) and sulphurized methyl linoleate; (11) the ether of (5), triphenyl phosphite and chloro-diphenylene oxide; (12) the ether from sodium thiocresolate and monochlorwax, and methyl dichlor stearate; (13) the ether of (5), a solution of naphthalene-chlorwax condensate in bright stock, sulphurized methyl esters of corn oil acids and tin phenyl stearate; (14) the ether of (5) and the ether from sodium thio naphtholate and the monochlor wax; (15) the ether of (5), the ether from sodium 8-hydroxy quinolate and the dichlor wax, sulphurized methyl linoleate and methyl dichlor stearate.  Other ethers described are obtained by reacting the monochlorwax with (1) sodium phenolate, (3) the potassium salt of a tetra-waxylated phenol, (6) the sodium salt of benzyl alcohol, (7) the calcium salt of o-chlorobenzyl alcohol, and (9) with sodium cyclohexanolate respectively, (4) by alkylating the ether of (1) with the monochlorwax and (8) by reacting sodium cresolate with the dichlorwax.  Further examples of lubricant additives mentioned are diphenylene oxide, chlorinated diphenyls, benzyl sulphide, tricresyl phosphate, tri-(2-ethylhexyl phenyl) phosphite, benzyl sulphone, diamyl xanthate, lauryl thiocyanate and metallic compounds such as chromium oleate, tetraphenyl lead, aluminium naphthenate, calcium cetyl 3 - isopropyl - 6 - methyl - 3 : 6 - endoethylene-4-tetrahydro phthalate and tin octadecyl phthalate. The Specification as open to inspection under Sect. 91, defines the ethers as those obtained as above described from paraffin hydrocarbons generally of at least 13 carbon atoms whose monochlor derivatives melt at lower temperatures than the hydrocarbons themselves and from compounds of the type R1XH where R1 is as defined above and X is an element in the right hand side of Group VI of the Periodic Table, e.g. O, S, Se or Te.  The paraffins may be derived from heavy ends of gasoline, kerosine, gas oil and paraffin wax.  F