GB694004A

GB694004A - Improvements in or relating to halogenated petroleum waxes

Info

Publication number: GB694004A
Application number: GB12197/51A
Authority: GB
Original assignee: Bataafsche Petroleum Maatschappij NV
Current assignee: Bataafsche Petroleum Maatschappij NV
Priority date: 1950-05-24
Filing date: 1951-05-24
Publication date: 1953-07-08
Also published as: GB709733A; DE967342C; US2682523A; BE503495A; DE929208C; FR1037448A; BE503494A; NL81706C

Abstract

A paraffin wax recovered from a mineral oil residue and having a melting-point of at least 160, preferably above 180 DEG F., an average molecular weight of above 475, preferably 525-1000, and containing at least 60, preferably at least 80, per cent by weight of straight-chain paraffins is halogenated to a halogen content of 20-60 per cent by weight. Crude waxy mineral oil of paraffinic or mixed base type is vacuum distilled, e.g. to remove all fractions boiling below 650 DEG F at 130 mm., and to leave a short residue fraction. This may be deasphalted and/or solvent extracted, and is then de-waxed by a solvent, the wax de-oiled by dissolving in the usual solvents, e.g. using 7 vols. to 1 of wax at a solution temperature of about 140 DEG F., and wax precipitated by cooling to about 60 DEG F. This wax is dissolved in 2-10 vols. of a de-waxing solvent at a temperature of at least the melting-point of the wax, generally about 150-170 DEG F., and the solution cooled to about 65-80 DEG F. below the melting-point of the wax desired to be precipitated. To recover high-melting wax, the filtration temperature must be, in general, about 100 DEG F. or more. Wax in solution may be recovered by distilling off solvent or precipitating at a lower temperature. Various wax fractions or combinations thereof having the stated characteristics may be used for the halogenation. Chlorine is preferred but fluorine, bromine or dis-similar halogens may be introduced. Thus, chlorine may be passed into the molten wax at 230-248 DEG F. to a content of 30 per cent, and the product blown with nitrogen. Halogenation may also be effected by the processes of U.S.A. Specifications 2,186,916, 2,340,968, 2,370,787, 2,372,414, and 2,403,179. Products containing chlorine, fluorine or both, the chlorine content being at least 80 per cent of the total halogen, are specified. The products are used as lubricants for metal working, in coating and protective agents, fireproofing and dielectric compositions, hydraulic fluids, fly-paper coating, plasticizers, and additives for cutting oils, lubricants, and greases. They may be added to neutral vehicles such as water, mineral, fatty or other oils, greases, polymers, and resins. They can be emulsified with water using partial esters of polyhydric alcohols and monocarboxylic acids as emulsifiers, with additions of cationic wetting-agents, detergents, oils, anti-oxidants, corrosion inhibitors, and the like. Partial esters of glycerine, erythritol, pentaerythritol, mannitol, sorbitol, and sorbitan with acids having an aliphatic or cycloaliphatic radical of at least 8, e.g. 10-40. carbon atoms are exemplified. They may be condensed with alkylene oxides or hydrogenated. The wetting agents include amines and their salts or amides, preferably having long-chain aliphatic radicals, and quaternary ammonium compounds. The emulsions may contain: 3-50 per cent halogenated wax, 1-25 emulsifier, 0.1-10 wetting agent, balance water. A base emulsion made by mixing the liquified wax with the other ingredients can be diluted with additional water or aqueous media. The compositions may include phosphatides, fatty or voltolized oils, sulphonates, metal stearates, phenates, alkyl or amino phenols, amines, long-chain dicarboxylic acids, compounds containing an acidic radical close to a mercapto, nitrile, nitro or nitroso group, urea or thiourea derivatives, carbazides, carbazones, polymerized olefins or esters. Examples are given of drawing lubricants containing 30-40 per cent chlorinated wax, 2-4 per cent sorbitan or glycerol mono-oleate, mannitan monolaurate or pentaerythritol monocaprylate, 4-8 polyoxyethylene sorbitan mono-oleate or stearate or polyoxyethylene mannitan monolaurate, 2-4 lauryl, stearyl, dodecyl, abietyl or oleyl amine or stearic amide, and balance water except in one case where 5 per cent mineral oil is included.ALSO:Lubricants, especially for metal working, comprise a product obtained from a paraffin wax recovered from a mineral oil residue and having a melting point of at least 160 DEG , preferably above 180 DEG F, an average molecular weight of above 475, preferably 525-1000, and containing at least 60, preferably at least 80 per cent by weight of straight-chain paraffins, by halogenating to a halogen content of 20-60 per cent by weight. Crude waxy mineral oil of paraffinic or mixed base type is vacuum distilled, e.g. to remove all fractions boiling below 650 DEG F at 130 mm., and to leave a short residue fraction. This may be de-asphalted and/or solvent extracted, and is then de-waxed by a solvent, the wax de-oiled by dissolving in the usual solvents; e.g. using 7 vols to 1 of wax at a solution temperature of about 140 DEG F, and wax precipitated by cooling to about 60 DEG F. This wax is dissolved in 2-10 vols. of a de-waxing solvent at a temperature of at least the melting point of the wax, generally about 150-170 DEG F, and the solution cooled to about 65-80 DEG F below the melting point of the wax desired to be precipitated. To recover high melting wax, the filtration temperature must be, in general, about 100 DEG F or more. Wax in solution may be recovered by distilling off solvent or precipitating at a lower temperature. Various wax fractions or combinations thereof having the stated characteristics may be used for the halogenation. Chlorine is preferred but fluorine, bromine or dissimilar halogens may be introduced (see Group IV(b)). The products are used as lubricants for metal working and additives for cutting oils, lubricants and greases. They may be added to neutral vehicles such as water, mineral, fatty or other oils, greases, polymers, and resins. They can be emulsified with water using partial esters of polyhydric alcohols and monocarboxylic acids as emulsifiers, with additions of cationic wetting agents, detergents, oils, anti-oxidants, corrosion inhibitors and the like. Partial esters of glycerine, erythritol, pentaerythritol, mannitol, sorbitol, and sorbitan with acids having an aliphatic or cycloaliphatic radical of at least 8, e.g. 10-40 carbon atoms are exemplified. They may be condensed with alkylene oxides or hydrogenated. The wetting agents include amines and their salts or amides, preferably having long chain aliphatic radicals, and quaternary ammonium compounds. The emulsions may contain: 3-50 per cent halogenated wax, 1-25 emulsifier, 0.1-10 wetting agent, balance water. A base emulsion made by mixing the liquefied wax with the other ingredients can be diluted with additional water or aqueous media. The compositions may include phosphatides, fatty or voltolized oils, sulphonates, metal stearates, phenates, alkyl or amino phenols, amines, long chain dicarboxylic acids, compounds containing an acidic radical close to a mercapto, nitrile, nitro or nitroso group, urea or thiourea derivatives, carbazides, carbazones, polymerized olefins or esters. Examples are given of drawing lubricants containing 30-40 per cent chlorinated wax, 2-4 per cent sorbitan or glycerol mono-oleate, mannitan monolaurate or pentaerythritol monocaprylate, 4-8 polyoxyethylene sorbitan monooleate or stearate or polyoxyethylene mannitan monolaurate, 2-4 lauryl, stearyl, dodecyl, abietyl or oleyl amine or stearic amide, and balance water except in one case where 5 per cent mineral oil is included.