Patent GB-701706-A (GB)
Title: An improved process for the preparation of lubricating oil additives
IPC: C07C2/86
Filed: 1951-05-07
Abstract: A process for the production of compounds suitable for use as additives for lubricants comprises mixing an aromatic compound, including a vinyl aromatic compound, with a halogenated aliphatic hydrocarbon and reacting the mixture with a separately formed complex compound formed by combining an aryl halide with a Friedel-Crafts metal halide catalyst.  When the aromatic compound is vinyl substituted the reaction may be carried out in two stages, during the first of which the temperature is kept low (e.g. at -20 DEG C. to room temperature) and the vinyl compound either in bulk or in an organic solvent is polymerised, and during the second stage the temperature is raised, e.g. to 50 DEG  to 80 DEG C. to complete the alkylation and acylation of the polymer.  The product may be isolated by removing the catalyst by adding an alcohol, treating with Attapulgus clay and then precipitating the product from its solution by adding it to a large volume of methanol or isopropanol.  Aromatic compounds mentioned are benzene, toluene, xylene, ethylbenzene, diphenyl, diphenylmethane, naphthalene, anthracene, phenanthrene, and phenol, cresol, naphthol, and ethers thereof.  As vinyl aromatic compounds there are specified styrene, a -methyl styrene, vinylnaphthalene, vinyl anthracene and vinyl carbazole.  The alkylating agents may be prepared (a) by replacing the -OH of alcohols by halogens, (b) by addition of halogen acids to unsaturated hydrocarbons or (c) by halogenation with or without Friedel-Crafts catalysts, of saturated hydrocarbons.  Specified are methyl chloride or bromide, ethyl chloride or fluoride, isopropyl chloride, amyl or hexyl chlorides, normal or iso-octyl chloride, 1-fluoro-2-methyl-propane, lauryl chlorides and fluorides, octadecyl chlorides and fluorides, and halogen derivatives of paraffin wax, petroleum, naphtha, kerosene, gas oil and lube oils.  If a single halo-alkane is used it preferably has the halogen atom not on a terminal carbon atom or p  contains two halogen atoms which may then be on terminal carbon atoms or on the carbon chain.  With mixed halo-alkanes it is preferred that a halo-alkane possessing at least two halogen atoms in the molecule is present in sufficient amount to cause a chain alkylation reaction and to yield a polymeric product. Chlorinated paraffin waxes of 20 to 30 carbon atoms with about 8 per cent. to 30 per cent. chlorine are preferred.  As acylating agents acid chlorides having 2 to 24 carbon atoms in the molecule are specified.  The complex may be formed by mixing the acid chloride with the catalyst in a solvent such as ethylene dichloride, nitromethane, nitrobenzene, or o-dichlorobenzene.  Friedel-Crafts catalysts mentioned are aluminium chloride, aluminium bromide, aluminium chlorobromide (Al Br2 Cl), aluminium bromochloride (Al Br Cl2), monochlor-aluminium pentabromide, monohydroxy aluminium pentabromide (AlBr2 OH. Al Cl3) aluminium iodobromide.  One or more molar quantities of the halo-alkane per mol. of aromatic hydrocrabon may be used.  The molar ratio of halo-alkane to acid chloride may be from about 1/0.01 to 1/2. Diluents for the reaction mixture may be used, e.g. Al Cl3 treated petroleum naphtha, ethylene dichloride, carbon disulphide, nitrobenzene, nitromethane and dichlorobenzene. In examples (1) a complex formed by mixing palmitoyl chloride and aluminium chloride in ethylene dichloride is reacted with a mixture of naphthalene and chlorinated wax; (2) a mixture of styrene and chlorinated wax is reacted at 50 DEG  to 80 DEG C. with a complex of aluminium chloride and acetyl chloride in ethylene dichloride.  In further examples the acetyl chloride of (2) is replaced by (3) lauroyl chloride, (4) myristoyl chloride, (5) palmitoyl chloride, and (6) stearoyl chloride.  Products containing side chains of different lengths may be preferable.  They may be physical mixtures or may be produced from mixed starting materials, e.g. mixed acid chlorides containing 12, 14, 16 and 18 carbon atoms as derived from coconut fatty esters.ALSO:A process for the production of compounds suitable for use as additives to lubricants comprises mixing an aromatic compound, including a vinyl aromatic compound, with a halogenated aliphatic hydrocarbon and reacting the mixture with a separately formed complex compound formed by combining an acyl halide with a Friedel-Crafts metal halide catalyst.  When the aromatic compound is vinyl substituted the reaction may be carried out in two stages, during the first of which the temperature is kept low (e.g., at -20 DEG C. to room temperature) and the vinyl compound is polymerized, and during the second stage the temperature is raised, e.g., to 50 DEG  to 100 DEG C. to complete alkylation and acylation of the polymer.  The product may be isolated by removing the catalyst by adding an alcohol, treating with Attapulgus clay and then precipitating the product from its solution by adding it to a large volume of methanol or isopropanol.  Aromatic compounds mentioned are benzene, toluene, xylene, ethylbenzene, diphenyl, diphenylmethane, naphthalene, anthracene, phenanthrene, and phenol, cresol, naphthol and ethers thereof.  As vinyl aromatic compounds are specified styrene, a -methylstyrene, vinylnaphthalene, vinyl anthracene and vinyl carbazole.  The alkylating agents may be prepared (a) by replacing the -OH of alcohols by halogens, (b) by addition of halogen acids to unsaturated hydrocarbons, or (c) by halogenation with or without Friedel-Crafts catalysts of saturated hydrocarbons. Specified are methyl chloride or bromide, ethyl chloride or fluoride, isopropyl chloride, amyl or hexyl chlorides, normal or iso-octyl chloride, 1-fluoro-2-methylpropane, lauryl chlorides and fluorides, octadecyl fluorides and chlorides, and halogen derivatives of paraffin wax, petroleum, naphtha, kerosene, gas oil and lube oils. If a single halo-alkane is used, it preferably has the halogen atom not on a terminal carbon atom or contains two halogen atoms which may then be on terminal carbon atoms or on the carbon chain. With mixed halo-alkanes, it is preferred that a halo-alkane possessing at least two halogen atoms in the molecule is present in sufficient amount to cause a chain alkylation reaction and to yield a polymeric product. Preferred are chlorinated paraffin waxes of 20 to 30 carbon atoms with about 8 per cent. to 30 per cent. chlorine by weight.  As acylating agents acid chlorides having 2 to 24, preferably 10 to 24, carbon atoms may be used. The complex may be formed by mixing the acid chloride with the catalyst in a solvent such as ethylene dichloride, nitromethane, nitrobenzene, o-dichlorbenzene. Friedel-Crafts catalysts mentioned are aluminium chloride, aluminium bromide, aluminium chlorobromide (AlBr2Cl), aluminium bromochloride (AlCl2Br), mono-chlor-aluminium pentabromide monohydroxy-aluminium pentabromide (AlBr2OH.AlCl3), and aluminium iodobromide.  One or more molar quantities of the haloalkane per mol. of aromatic hydrocarbon may be used.  The molar ratio of halo-alkane to acid chloride may be from about 1/0.01 to 1/2 .  Diluents for the reaction mixture may be used, e.g. AlCl3 treated petroleum naphtha, ethylene dichloride, carbon disulphide, nitrobenzene, nitromethane and dichlorobenzene. In examples (1) a mixture of a complex formed by mixing palmitoyl chloride and aluminium chloride in ethylene dichloride is reacted with a mixture of naphthalene and chlorinated wax; (2) a mixture of styrene and chlorinated wax is reacted at 50 DEG  to 80 DEG  C. with a complex of acetyl chloride and aluminium chloride in ethylene dichloride.  In further examples the acetyl chloride of (2) is replaced by (3) lauroyl chloride; (4) myristoyl chloride; (5) palmitoyl chloride and (6) stearoyl chloride.  Products containing side chains of different lengths may be preferable.  They may be physical mixtures or may be produced from mixed starting materials, e.g. mixed acid chlorides p  containing 12, 14, 16, and 18 carbon atoms as derived from coconut fatty esters.ALSO:A process for the production of compounds for use as additives for lubricants comprises mixing an aromatic compound, including a vinyl aromatic compound, with a halogenated aliphatic hydrocarbon and reacting the mixture with a separately formed complex compound formed by combining an acyl halide with a Friedel-Crafts metal halide catalyst.  When the aromatic compound is vinyl substituted the reaction may be carried out in two stages, during the first of which the temperature is kept low (e.g. at -20 DEG C. to room temperature) and the vinyl compound is polymerised, and during the second stage the temperature is raised, e.g. to 50 DEG  to 80 DEG C. to complete the alkylation and acylation of the polymer.  Aromatic compounds specified are benzene, toluene, xylene, ethylbenzene, diphenyl, diphenylmethane, naphthalene, anthracene, phenanthrene, and phenol, cresol, naphthol and ethers thereof.  Vinyl aromatic compounds specified are styrene, a -methylstyrene, vinyl naphthalene, vinyl anthracene and vinyl carbazole.  The alkylating agents may be prepared (a) by replacing the -OH of alcohols by halogen, (b) by addition of halogen acids to unsaturated hydrocarbons, (c) by halogenation with or without Friedel-Crafts catalysts of saturated hydrocarbons.  Specified are methyl chloride or bromide, ethyl chloride or fluoride, isopropyl chloride, amyl or hexyl chlorides, normal or iso-octyl chloride, 1-fluoro-2-methylpropane, lauryl chlorides or fluorides, octadecyl chlorides and fluorides and halogen derivatives of paraffin wax, petroleum naphtha, kerosene, gas oil and lube oils.  Chlorinated paraffin waxes of 20 to 30 carbon atoms with about 8 per cent. to 30 per cent. chlorine are preferred.  As acylating agents acid chlorides having 2 to 24 carbon atoms in the molecule are specified.  One or more molar quantities of the halo-alkane per mol of aromatic hydroc