Patent GB-608214-A (GB)
Title: An improved manufacture of hydrocarbon oil compositions
IPC: C10M161/00
Filed: 1942-04-28
Abstract: Lubricating and other oils are rendered non-corrosive by adding a small proportion of an oil-soluble resinous auto-condensation and/or polymerization product of a hydroxy-aryl-alkyl amine of the general formula HO-Ar-CH2-NR1R2, where Ar is an aromatic nucleus, preferably alkylated with an alkyl radical of 4 to 20 carbon atoms such as iso-octyl, and R1R2 are alkyl or aryl radicals or hydrogen.  Other known addition agents may be added.  The resinous body is particularly effective with extreme pressure lubricants containing corrosive chlorine compounds, such as chlorinated paraffin wax, and derivatives in which a portion of the chlorine has been replaced by sulphur as in sulphurised chlorinated naphtha or in which other sulphur compounds have been incorporated.  Comparative results of tests for corrosion, oxidation, sediment deposition and colour stability are given for oils containing resins obtained from iso-octyl phenol, formaldehyde and ammonia, from iso-octyl hydroxy benzyl diethyl amine, from ammonia and chlormethyl diisobutyl phenol, from ammonia and chlormethyl diamyl phenol, and from dicyclo hexyl amino methyl diamyl phenol.  The amount of the resinous oil-soluble organic base to be added varies from 0.01 per cent to 1 or 2 per cent according to the type of lubricant and the amount of chlorine or sulphur or other corrosive elements therein, but generally an amount of 0.05 to 0.5 per cent is suitable.  If phenols extracted from petroleum oils, or formed by alkylation of phenols with olefines such as occur in cracked petroleum fractions, or other high molecular weight complex alkyl phenolic products are reacted with aldehyde and a nitrogen base as described, resinous products which are effective in reducing the pour point of waxy oils and in improving the viscosity index of lubricating oils as well as improving their film strength, stability and resistance to oxidation are obtained.  Apart from lubricating oils, the resinous addition agents may be added to turbine oils, cutting oils, fuel oils, white oils, slushing oils, gasoline, and waxes.  The resinous products may be prepared by condensing together a phenol, formaldehyde and ammonia, or an alkyl or aryl amine, heating and allowing to stand, or the phenol and formaldehyde may be condensed with a hydrogen halide and the product treated with ammonia, or an amine, and heated or resinified by standing; alternatively, the formaldehyde may be first condensed with the ammonia or amine and the product then heated under pressure with the phenol (see Group IV (a)).  The oil solubility of the products increases with the degree of condensation or resinification and also with the length of the alkyl substituent in the phenol nucleus. Other addition agents which may be incorporated in the compositions include fatty acid and naphthenic acid soaps, fatty oils, synthetic esters, sulphur and halogen compounds for increasing oiliness and film strength, thickeners such as polyisobutylene, and oil-soluble metal soaps especially of the alkaline earth metals.ALSO:Addition agents for lubricating and other oils comprise oil-soluble auto-condensation and/or polymerization products of hydroxyaryl-alkyl amines of the general formula HO-Ar-CH2NR1R2, where Ar is an aromatic nucleus, preferably alkylated with an alkyl radical of 4 to 20 carbon atoms such as isooctyl, and R1, R2 are alkyl or aryl radicals or hydrogen.  They may be prepared by condensing together a phenol, formaldehyde, and ammonia or an alkyl or aryl amine, heating, and allowing to stand, or the phenol and formaldehyde may be condensed with a hydrogen halide and the product treated with ammonia, or an amine, and heated or resinified by standing; alternatively, the formaldehyde may be first condensed with the ammonia or amine and the product then heated under pressure with the phenol.  In an example a solution of para-iso-octyl phenol in benzene is slowly run into a solution of paraformaldehyde in concentrated hydrochloric acid with stirring and continuous passage of dry hydrochloric acid gas through the mixture.  The upper benzene layer, containing a viscous light-red oil is then slowly treated with anhydrous ammonia dissolved in isopropyl alcohol.  A thick yellow slurry containing excess of ammonia is obtained which is sealed in a stainless steel bomb and heated to 110 to 120 DEG  C. for 20 hours. Evaporation of the benzene produced a brittle, resinous material containing 2.8 per cent nitrogen.  In an alternative process, hydrogen chloride and formaldehyde are first reacted to form bis-chlormethyl ethers such as Cl CH2OCH2 Cl and Cl CH2(OCH2)n OCH2Cl and the mixture reacted with the alkyl phenol, and then with ammonia.  In a further method the alkyl phenol is converted to sodium salt which is reacted with aldehyde to give an alkylol derivative.  This may be converted to the chloride by reaction with hydrogen chloride and the product reacted with ammonia.  In a further method, the iso-octyl phenol, aqueous formaldehyde, and concentrated aqueous ammonia are quickly sealed in a stainless steel bomb and heated to 120 DEG  C. for 16 hours.  A soft red resin containing 1.3 per cent nitrogen is obtained.  More complex derivatives of hydroxy benzyl chloride such as <FORM:0608214/IV(a)/1> may be reacted with ammonia or primary or secondary amines to produce resinous products according to the invention.  In another example, diethyl amino methyl iso-octyl phenol (C2H5)2NCH2,C8H17C6H\t 3OH is prepared by reacting ethoxy methyl diethyl amine (C2H5)2 NCH2OC2H5 with iso-octyl phenol on the steam bath for 24 hours and distilling under 3 mm. pressure giving a yellow, transparent hard resin. Other resins are prepared from ammonia and chloromethyl diamyl phenol, and from dicyclohexylamino methyl diamyl phenol.  The phenols to be used include generally all nuclearly hydroxylated aromatic compounds having phenolic properties and a readily replaceable nuclear hydrogen atom ortho or para to the hydroxy group.  Phenols extracted from petroleum oils and naturally occuring phenols such as cardinol from cashew nuts may also be used. The alkyl substituent may include chlorinated paraffin wax, chlorinated petrolatums, and sulphurised chlorinated kerosene. The effects of adding resins according to the invention to various oils are desscribed (see Group III).  The Specification as open to inspection under Sect. 91 states that primary and secondary amines such as diethyl amine, diamylamine, piperidine, aniline, diphenyl amine, and substituted amines such as ethanolamine may be substituted for ammonia in any of the processes described.  This subject matter does not appear in the Specification as accepted.ALSO:Addition agents for lubricating and other oils comprise oil-soluble auto-condensation and/or polymerization products of hydroxyaryl-alkyl amines of the general formula HO-Ar-CH2-NR1R2, where Ar is an aromatic nucleus, preferably alkylated with an alkyl radical of 4 to 20 carbon atoms such as iso-octyl, and R1, R2 are alkyl or aryl radicals or hydrogen. They may be prepared by condensing together a phenol, formaldehyde and ammonia or an alkyl or aryl amine, heating and allowing to stand, or the phenol and formaldehyde may be condensed with a hydrogen halide and the product treated with ammonia, or an amine, and heated or resinified by standing; alternatively, the formaldehyde may be first condensed with the ammonia or amine and the product then heated under pressure with the phenol.  In an example, a solution of para-iso-octyl phenol in benzene is slowly run into a solution of paraformaldehyde in concentrated hydrochloric acid with stirring and continuous passage of dry hydrochloric acid gas through the mixture. The upper benzene layer, containing a viscous light red oil, is then slowly treated with anhydrous ammonia dissolved in isopropyl alcohol. A thick yellow slurry containing excess of ammonia is obtained which is sealed in a stainless steel bomb and heated to 110 DEG  to 120 DEG C. for 20 hours. Evaporation of the benzene produced a brittle, resinous material containing 2.8 per cent nitrogen.  In an alternative process, hydrogen chloride and formaldehyde are first reacted to form bischlormethyl ethers such as ClCH2OCH2Cl and ClCH2(OCH2)nOCH2Cl and the mixture reacted with the alkyl phenol, and then with ammonia.  In a further method, the alkyl phenol is converted to sodium salt which is reacted with aldehyde to give an alkylol derivative.  This may be converted to the chloride by reaction with hydrogen chloride and the product reacted with ammonia. In a further method, the isooctyl phenol, aqueous formaldehyde and concentrated aqueous ammonia are quickly sealed in a stainless steel bomb and heated to 120 DEG  C. for 16 hours.  A soft red resin containing 1.3 per cent nitrogen is obtained.  More complex derivatives of hydroxy benzyl chloride such as <FORM:0608214/IV(b)/1> may be reacted with ammonia or primary or secondary amines to produce resinous products according to the invention.  In another example, diethyl amino methyl iso-octyl phenol (C2H5)2NCH2.C8H17C6 H3OH is prepared by reacting ethoxy methyl diethyl amine (C2H5)2 NCH2OC2H5 with iso-octyl phenol on the steam bath for 24 hours and distilling under 3 mm. pressure, giving a yellow, transparent, hard resin. Other resins are prepared from ammonia and chlormethyl diamyl phenol, and from dicyclo hexylamino methyl diamyl phenol.  The phenols to be used include generally all nuclearly hydroxylated aromatic compounds having phenolic properties and a readily replaceable nuclear hydrogen atom ortho or para to the hydroxyl group.  Phenols extracted from petroleum oils and naturally occurring phenols such as cardinol from cashew nuts may also be used.  The alkyl substituent may include chlorinated paraffin wax, chlorinated petrolatums and sulphurised chlorinated kerosene. The effects of adding resins according to th