US3108958A - Lubricant additive and composition containing same - Google Patents
Lubricant additive and composition containing same Download PDFInfo
- Publication number
- US3108958A US3108958A US778576A US77857658A US3108958A US 3108958 A US3108958 A US 3108958A US 778576 A US778576 A US 778576A US 77857658 A US77857658 A US 77857658A US 3108958 A US3108958 A US 3108958A
- Authority
- US
- United States
- Prior art keywords
- acid
- moles
- product
- reaction product
- polyamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/123—Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/04—Reaction products of phosphorus sulfur compounds with hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
- C10M2225/041—Hydrocarbon polymers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/09—Complexes with metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- This invention relates to additive compositions for use in lubricating oils, the use of such additive compositions, and improved lubricating compositions containing such additive compositions and intended for use in internal combustion engines such as diesel engines and automobile engines. More particularly the invention relates to additive compositions which impart deter ency and anti-rust properties to lubricating oils and suppress excess varnish formation when used in lubricating oils.
- a hydrolyzed phosphorus sulfide-hydrocarbon reaction product may be reacted with an amine compound and a fiuoroboric acid such as ditluorobori-c acid to form a new composition of matter with desirable characteristics for use as an additive composition in a lubricating oil.
- a fiuoroboric acid such as ditluorobori-c acid
- the boron, fluorine and amine-containing additive composition of our present invention overcomes the problems of the mineral lubricating oil in its use without additives by imparting to the lubricating oil high detergency properties and eliminating excessive varnish formation and corrosion.
- the new additive may also be used in an additive concentrate in amounts of from to 50 weight percent or more for addition to lubricating oils.
- our present invention provides an additive composition for lubricating oils formed by reacting a hydrolyzed phosphorus sulfide-hydrocarbon reaction product with at least a sur'licient amount of an amine compound to neutralize the reaction product and then reacting the resulting neutralized reaction product with a fluoroboric acid such as difiuoro boric acid and monofluoroboric acid.
- a fluoroboric acid such as difiuoro boric acid and monofluoroboric acid.
- Our invention also provides an improved mineral oil containing an effective amount of our additive composition to impart improved properties to the lubricating oil.
- the amine compound used in preparing the additive composition of our present invention may be any aliphatic or substituted aliphatic compound having 1 or more basic amine groups.
- Preferred amine compounds particularly suited for use in the preparation or" the additive compo sition of our present invention are the hydroxy aliphatic amines such as monohydroxy, dihydroxy, and polyhydroxy aliphatic amines and particularly preferred are the aliphatic polyamines such as diamines, triamines, etc., having two or more carbon atoms in the aliphatic chain.
- Polyhydroxy aliphatic polyamines are includable in either group.
- Particularly suitable aliphatic polyamines are alkylcne polyarnines containing at least two primary amino nitrogen atoms.
- alkylene polyamines suitable for the hereindesoribed purpose are ethylene diamine, propylene diamine, diethylene-triamine, diamylene triamine, triethylene tetramine, tripropylene tetramine, diethylene-propylene tetramine, tetraethylene pentamine, tetrabutylene pentamine, diethylendipropylene pentamine, butylene diamine, dihexylene triamine, and the like, or mixtures thereof.
- a suitable polyamine product is a crude diethylene triamine containing minor amounts of ethylene diamine and tricthylene tetramine.
- Suitable aliphatic polyamines include those having the general formula RNH(CH NH in which R is preferably a C to C aliphatic chain, and which are obtained by condensing the suitable amine with *acrylonitrile arid hydrogenating to the corresponding diamine.
- Commercially available aliphatic polyamines of this type are those marketed by Armour and Company as Duo meens, which are prepared by the condensation of a dodecyl (coco) amine or an octadecyl (tallow) amine with acrylonitrile followed by hydrogenation to the corresponding diamine product; these products are marketed as Duomeen C and Duorneen T, respectively.
- the diflucro-boric acid a liquid, may be conveniently prepared by reacting B 0 with hydrogen fluoride as taught by F. 5. Sowa et al, EACS 57,454 (1935).
- the hydrolyzed phosphorus sulfide-hydrocarbon reaction product may be prepared by any method known to the prior art. We prefer to react a hy'clrocanbon with from about 1% to about 50%, and preferably from about 5% to about 25% of phosphorus sulfide at a temperature of from about 290 F. to about 600 F. in a non-oxidizing atmosphere, as, for example, in a nitrogen atmosphere. The reaction is carried out for from about one to about ten hours or more, and preferably for about five h-curs. The reaction may be carried out in the presence of a sulfurizing agent such as sulfur, sulfur chlorides, etc, if desired. The product is hydrolyzed rat a temperature of from about 200 F.
- the hydrolyzed product may be solvent extracted to remove salts of inorganic phosphorus acids and low molecular Weight organic phosphorus acids formed during hydrolysis. Solvent extraction may be accomplished in accordance with the method described by Norman E. Le-mrnon et al. in US. 2,843,579, issued July 15, 1958.
- any phosphorus sulfides such as as, P 3 P 3 or other phosphorus sulfides and preferably phosphorus pentasulfide, P 8 may be reacted with a hydrocarbon.
- the hydrocarbons used in the phosphorus sulfidehydrocarbon reaction may be polymers such as monoolefin polymers, copolymers, graft polymers, etc. and may also be unpolymerized or unpolymerizable hydrocarbons such as olefins, parafiins, cycloparailins, aromatic hydrocarbons, etc.
- the mono-olefin polymer to be treated may' be the polymer resulting from the polymerization of low molecular weight mono-olefins preferably the isomonoolefins, such as iso'butylene and isoarnylene and/ or the copolymers obtained by the polymerization of hydrocarbon mixtures containing isomono-olefins and mono-olefins of less than six carbon atoms and preferably those of four carbon atoms.
- the polymer may be obtained by the polymerization of these olefins or mixed olefins in the presence of catalysts such as sulfuric acid, phosphoric acid, or boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel-Crafts type.
- the polymers advantageously have molecular weights ranging from about 150 to about 50,000 or more, and preferably from about 500 to about 10,000.
- a starting material there can be used the polymer or synthetic lubricating oil obtained by polymerizing the unsaturated hydrocarbons resulting from the vapor phase cracking of paraffin waxes in the presence of aluminum chloride which is fully described in US. Patents Nos. 1,955,260; 1,970,402; and 2,091,398.
- Still another type of olefin polymer which may be employed is the polymer resulting from the treatment of vapor phase cracked gasoline and/ or gasoline fractions with sulfuric acid or solid adsorbents, such as fullers earth, whereby the unsaturated polymerized hydrocarbons are removed.
- the treatment with phosphorous sulfide of the polymers resulting from the voltolization of hydrocarbons as described for example in US. Patents Nos. 2,197,768 and 2,191,787.
- hydrocarbons which we can use as reactants in the preparation of the phosphorus sulfide reaction prod not are parafijns, olefins, aromatics or alkyl aromatics, cyclic aliphatics, petroleum fractions, such as lubricating oil fractions, petrolatums, waxes, cracking cycle stocks, condensation products of the foregoing hydrocarbons, solvent extracts of petroleum extracts, etc.
- the parafi'in hydrocarbons can be those obtained from petroleum oils such as bright stock residuums, lubricating oil distillates, petrolatums, or parafiin waxes. We may also halogenate any of the foregoing paraflins and condense the same with aromatic hydrocarbons in the presence of anhydrous inorganic halides such as aluminum chloride, zinc chloride, boron fluoride and the like.
- high molecular weight olefinic hydrocarbons which we may employ as reactants are cetene (C cerotene (C melene (C and mixed high molecular weight algenes obtained by cracking petroleum oils.
- olefins suitable for the preparation of the herein described phosphorus sulfide reaction products are olefins having at least carbon atoms in the molecular of which from about 13 carbon atoms to about 18 carbon atoms, and preferably at least 15 carbon atoms in a long chain.
- Such olefins can be obtained by the dehydrogenation of paraffins, such as by the cracking of paraffin waxes or by the dehalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated parafiin waxes.
- any of the hydrocarbons recited as useable by Norman E. Lemmon et al. in US. 2,843,579, issued July 15, 1958, may be employed herein.
- the additive composition concentrates of our present invention are formed by neutralizing a hydrolyzed phosphorus sulfide-hydrocarbon reaction product, formed, for example, as indicated above and preferably solvent extracted, with an amine compound having 2 or more carbon atoms and preferably an aliphatic polyamine as defined above.
- the neutralized product is then reacted with difiuoroboric acid preferably in amounts corresponding to from about 1 to about 3 moles boron per mole of neutralized product.
- amine compound per mole of acid phosphorous in the hydrolyzed reaction product depending on the type of amine compound used. It is preferred to neutralize only one amine group of a given amine compound and, therefore, from about 1 to about 1.1 moles of the amine compound per mole of acid phosphorus is preferred. No solvent is necessary for the reaction since difiuoroooric acid is a liquid which is sufficiently soluble in the reaction mixture. During the difluoroboric acid reaction, it may be advantageous to stir the mixture of neutralized reaction product and difiuoroboric acid and to warm the mixture for a short period of time, for example about one hour, to increase the solubility of the difluoroboric acid.
- reaction mixture is then heated to a temperature above C. to strip off water and allow the reaction to go to completion.
- a temperature above C. we have found that when water is not stripped 01f the reaction is reversible and will not go to completion due to the instability of the reaction product in the presence of water.
- the reaction mixture should not be heated to a temperature at which the amine is driven from the mixture. If temperatures higher than the boiling point of the amine are used means for retaining the amine, such as, for example, refluxing, should be employed.
- the product should be hazy due to the presence of impurities, for example the presence of excess difluoroboric acid which has not reacted with the neutralized phosphorus sulfide hydrocarbon reaction product or has not dissolved therein, it may be desirable to filter the product through diatomaceous earth to obtain a suitably clear product.
- the products formed in the above boron reaction contain chemically bonded boron and fluorine.
- the additive composition may be used in lubricating oils in varying amounts constituting minor proportions of the total lubricating composition.
- the amount of additive used should be in excess of 0.1 weight percent.
- the additive is efiective in imparting improved detergency lubricating oils even when used in such small amounts as range from about 0.1 weight percent.
- the additive when used in a lubricating oil in an internal combustion engine was also found to suppress the octane requirement increase of the engine probably by entering the combustion chamber by the process of blow-by.
- a hydrolyzed phosphorus sulfide-hydrocarbon reaction product is prepared by reacting about 15.5 wt. percent P S with a butylene polymer having a molecular weight of about 750-800 at a temperature of about 450 F. in a nitrogen atmosphere. The reaction is continued for about five hours for product formation. The product has a phosphorus content of about 4.3% and a sulfur content of about 7.5%. The reaction product formed is then hydrolyzed with steam at a temperature of about 300 F. to about 400 F.
- the hydrolyzed product was diluted, for ease of handling, to about a 60% concentrate with a solvent extracted Mid-Continent 5W mineral oil having a viscosity of about 38 SSU at 210 F.
- the product was then contacted with clay (fullers earth) and filtered to remove inorganic impurities.
- the resulting clay treated product was used as a starting material for the preparation of additives in subsequent examples.
- the basic salt was treated with 253 grams (3 moles) of difiuoroboric acid (E B- 13.1 159 C.) with stirring at 100 C. for four hours and 1320 grams of solvent extracted Mid- Continent 5W mineral oil having a viscosity of about 38 SSU at 210 F. were then added.
- the reaction mixture was filtered through Celite. The filtrate was a bright, brown, oil-soluble product which had a boron content of 0.35 wt. percent, a nitrogen content of 1.35 wt. percent, a phosphorus content of 1.16 wt. percent and a fluorine content of 2.0 wt. percent.
- Example 11 2035 grams (1.24 moles) of the clay contacted hydrolyzed intermediate were reacted with 199 grams (1.36 moles, 1.1 moles per mole of intermediate) of triethylenetetramine and a basic salt was formed.
- the basic salt was treated with 296 grams (3.53 moles) of difiuoroboric acid (H BO F B.-P. 159 C.) with stirring at 100 C. for four hours and 1059 grams of solvent extracted Mid-Continent 5W mineral oil having a viscosity of about 38 SSU at 210 F were then added.
- the reaction mixture was blown with nitrogen at 125 F. and zfiltered through Celite.
- the filtrate was a bright, brown, oil-soluble product which had a boron content of 0.78 wt. percent, a nitrogen content of 1.77 wt. percent, a phosphorus content of 1.23 wt. percent and a fluorine content of 2.7 wt. percent.
- Example 111 2000 grams (1.22 moles) of the clay contacted hydrolyzed intenmediate were reacted with 537 grams (1.34 moles, 1.1 moles per mole of intermediate) or" Duomeen T and a basic salt was formed.
- Duomeen T commercially prepared by Armour Chemical Division, Chicago, Illinois, is predominantly a propylene diarnine having a side chain derived from tallow-fatty acid and melting in the range of from about 44 C. to about 48 C.; the side chain is attached directly to the one nitrogen atom.
- the basic salt was treated with 125 grams (1.49 moles) of difluoroboric acid (H BO F 13.1. 159 C.) with stirring at 100 C.
- the eifectivcness of the products of the present invention in improving the detergency characteristics of lubricating oils is demonstrated by the data in Table I.
- the data were obtained by subjecting a commercial-type lubricating oil with and without the product of the above example to the detergency and oxidation test known as the Squalene Indiana Stirring Oxidation Test (1.8.0.11).
- Squalene I.S.O.T. by weight of squalene (a highly unsaturated reactive hydrocarbon that polymerizes easily and forms a tightly adhering varnish during the test) is added to the oil to be tested and the mixture is heated at 300 F. in a 500- cc.
- Varru'sh rating A 4 to 5 A composition of the present invention was comparatively subjected to a Detergency Screening Test which rates detergency by a determination of piston varnish deposits.
- the test was carried out in a current model Chevrolet Powerglide Engine operating for one hour at 500 r.p.m. and no load and for 6 subsequent hours at 2500 rpm. and a load of 3.1-1.1.
- the oil temperature for the first hour was F, for the second and third hours was F. and for the 4 remaining hours was 220 F.
- the water temperature @501 the first 3 hours was from 85 to 95 F. and for the remaining 4 hours was to 180 F.
- Each 7 hours so constituted is regarded a cycle.
- composition of the present invention indicated as Sample B gave superior piston varnish rating results in comparison with metalcontaining detengent additives as exemplified by Samples C and D when compounded in commercial-type lubricants and also gave superior results in comparison with the very low piston varnish rating of the lubricant Without any detergent additive as exemplified by Sample A.
- compositions of the present invention can be used as indicated above in varying amounts of from 0.1 up to about 15 percent in lubri- For comparison of metal-containing phosphorus sulfidehydrocarbon reaction products with the amine-containing fluoroboric acid complexes.
- lubricating oil bases can be used, such as hydrocarbon oils, both natural and synthetic, for example, those obtained by the polymerization of olefins, as well as synthetic lubricating oils of the alkylene oxide type and the polycarboxylic acid ester type, such as the oil soluble esters of adipic acid, sebacic acid, azelaic acid, etc. It is also contemplated that various other well known additives, such as antioxidants, anti-foaming agents, pourpoint depressors, extreme pressure agents, antiwear agents, may be incorporated in lubricating oils containing the additives of our invention.
- Concentrates of a suitable oil base containing more than percent, for example up to 50 percent or more, of the additives of this invention alone or in combination with other additives can be used for blending with hydrocarbon oils or other oils in the proportions desired for the particular conditions of use to give a finished lubricating product containing the additives of this invention.
- an oil-soluble detergent neutralized reaction product prepared by the process comprising: reacting a phosphorus sulfide with a hydrocarbon; hydrolyzing the resulting phosphorus sulfidehydrocarbon reaction product; and reacting the hydrolyzed product with fluoroboric acid in an amount corresponding to from about one to about three moles of boron per mole of reaction product and an aliphatic polyamine having from 2 to 21 carbon atoms in the aliphatic group in an amount corresponding to from about one to about 1.1 moles of polyamine per mole of acid phosphorus, at a temperature below the temperature at which said polyamine is driven from the mixture of reactants.
- a lubricating composition comprising a major amount of hydrocarbon lubricating oil and from about 0.1 to about weight percent of the composition of claim 1.
- composition of claim 1 wherein the aliphatic polyamine is diethylenetriamine.
- composition of claim 1 wherein the aliphatic polyamine is a propylene diamine having a side chain derived from taliow-fatty acid and melting in the range of 44 to 48 C.
- composition of claim 1 wherein the aliphatic polyamine is triethylene tetramine.
- an oil-soluble detergent neutralized reaction product prepared by the process comprising the steps of: reacting a phosphorus sulfide with a hydrocarbon; hydrolyzing the resultant phosphorus sulfide-hydrocarbon reaction product; neutralizing the hydrolyzed product with an aliphatic polyamine having from 2 to 21 carbon atoms in the aliphatic group in an amount corresponding to from about one to about 1.1 moles of polyamine per mole of acid phosphorus; and reacting the neutralized product with fluoroboric acid in an amount corresponding to from about one to about three moles of boron per mole of reaction product at a temperature below the temperature at which said polyamine is driven from the mixture of reactants.
- a lubricating composition comprising a major amount of hydrocarbon lubricating oil and from about 0.1 to about 20 weight percent of the composition of claim 6.
- an oil-soluble de tergent neutralized reaction product prepared by the process comprising the steps of: reacting 'a phosphorus sulfide with a hydrocarbon; hydrolyzing the resultant phosphorus sulfide-hydrocarbon reaction product; reacting fluoroboric acid in an amount corresponding to from about one to about three moles of boron per mole of reaction product with an aliphatic polyamine having from 2 to 21 carbon atoms in the alkylene group and containing at least two primary amino nitrogen atoms in an amount corresponding to from about one to about 1.1 moles of polyamine per mole of acid phosphorus; and reacting the resulting reaction product with a hydrolyzed phosphorus sulfidehydrocarbon reaction product at a temperature below the temperature at which the polyamine is driven from the mixture of reactants.
- an oil-soluble detergent neutralized reaction product prepared by the process comprising the steps of: reacting phosphorus sulfide with a hydrocarbon; hydrolyzing the resulting phosphorus sulfide-hydrocarbon reaction product; neutralizing the resulting hydrolyzed product with from about one to about 1.1 moles of ethylene diamine per mole of hydrolyzed reaction product; and reacting the resulting neutralized product with from about one to about three moles based on boron of fluoroboric acid per mole of neutralized product at a temperature below the temperature at which the ethylene diamine is driven from the mixture of reactants.
- an oil-soluble detergent neutralized reaction product prepared by the process comprising the steps of: reacting phosphorus sulfide with a butene polymer at a temperature of from about 200 F. to about 600 F. hydrolyzing the resulting phosphorus sulfide-butene polymer reaction product; neutralizing the resulting hydrolyzed product with from about one to about 1.1 moles per mole of hydrolyzed reaction product of an alkylene polyamine having the formula RNH(CH NH wherein R is a C to C aliphatic chain; reacting the resulting neutralized product with from about one to about three moles based on boron of fluoroboric acid per mole of neutralized product at a temperature below the temperature at which the polyamine is driven from the mixture of reactants; and heating the reactants to a temperature above C. whereby water is stripped from the reaction mixture.
- a lubricant additive concentrate consisting essentially of a hydrocarbon lubricating oil containing more than about 10% of an oil-soluble detergent neutralized reaction product prepared by the process comprising: reacting a phosphorus sulfide with a hydrcarbon; hydrolyzing the resulting phosphorus sulfide-hydrocarbon reaction product; and reacting the hydrolyzed product with fluoroboric acid in an amount corresponding to from about one to about three moles of boron per mole of reaction product and an aliphatic polyamine having from 2 to 21 carbon atoms in the aliphatic group in an amount corresponding to from about one to about 1.1 moles of polyamine per mole of acid phosphorus, at a temperature below the temperature at which the polyamine is driven from the mixture of reactants.
Description
United States Patent 3,198,958 LUilRlCANT ADEHTIVE AND CilaMlt'l lllibN CQN'HAENING SAME Donald L. Klass, Barrington, ill, and Roger W. Watson, Highland, ind, assignors to Standard Gil Company, Chicago, Ell, a corporation of Indiana No Drawing. Filed Dec. 8, 1958, Sea. No. 778,576 11 Claims. (Qt. 252-4217) This invention relates to additive compositions for use in lubricating oils, the use of such additive compositions, and improved lubricating compositions containing such additive compositions and intended for use in internal combustion engines such as diesel engines and automobile engines. More particularly the invention relates to additive compositions which impart deter ency and anti-rust properties to lubricating oils and suppress excess varnish formation when used in lubricating oils.
Straight petroleum lubricants are effective Within certain defined limits of engine operating conditions and when these limits are exceeded, such lubricants frequently fail to give the desired performance demanded of them. Since, in modernengines designed to give increased performance, these limits are frequently exceeded, th use of straight mineral oils as lubricants produce undesirable conditions within the engine; thus varnish formation and corrosion are excessive in modern engines using mineral oils alone.
It is an object of the present invention to provide a new composition for use as a lubricant additive. it is another object to provide a lubricating oil additive composition which imparts detergency, anti-varnish formation and anti-rust properites to a lubricating oil. It is a further object of the present invention to provide a lubricating oil having these properties and suitable for use in a modern internal combustion engine. Other objects and advantages of our present invention will be apparent from the descriptions and examples set out below.
We have discovered that a hydrolyzed phosphorus sulfide-hydrocarbon reaction product may be reacted with an amine compound and a fiuoroboric acid such as ditluorobori-c acid to form a new composition of matter with desirable characteristics for use as an additive composition in a lubricating oil. When used in a lubricating oil in even very small amounts, i.e. in amounts as low as 0.1 wt. percent and preferably not exceeding 20 wt. percent, the boron, fluorine and amine-containing additive composition of our present invention overcomes the problems of the mineral lubricating oil in its use without additives by imparting to the lubricating oil high detergency properties and eliminating excessive varnish formation and corrosion. The new additive may also be used in an additive concentrate in amounts of from to 50 weight percent or more for addition to lubricating oils.
Broadly, our present invention provides an additive composition for lubricating oils formed by reacting a hydrolyzed phosphorus sulfide-hydrocarbon reaction product with at least a sur'licient amount of an amine compound to neutralize the reaction product and then reacting the resulting neutralized reaction product with a fluoroboric acid such as difiuoro boric acid and monofluoroboric acid. Our invention also provides an improved mineral oil containing an effective amount of our additive composition to impart improved properties to the lubricating oil.
The amine compound used in preparing the additive composition of our present invention may be any aliphatic or substituted aliphatic compound having 1 or more basic amine groups. Preferred amine compounds particularly suited for use in the preparation or" the additive compo sition of our present invention are the hydroxy aliphatic amines such as monohydroxy, dihydroxy, and polyhydroxy aliphatic amines and particularly preferred are the aliphatic polyamines such as diamines, triamines, etc., having two or more carbon atoms in the aliphatic chain. Polyhydroxy aliphatic polyamines are includable in either group. Particularly suitable aliphatic polyamines are alkylcne polyarnines containing at least two primary amino nitrogen atoms. Examples of alkylene polyamines suitable for the hereindesoribed purpose are ethylene diamine, propylene diamine, diethylene-triamine, diamylene triamine, triethylene tetramine, tripropylene tetramine, diethylene-propylene tetramine, tetraethylene pentamine, tetrabutylene pentamine, diethylendipropylene pentamine, butylene diamine, dihexylene triamine, and the like, or mixtures thereof. For example, a suitable polyamine product is a crude diethylene triamine containing minor amounts of ethylene diamine and tricthylene tetramine. Other suitable aliphatic polyamines include those having the general formula RNH(CH NH in which R is preferably a C to C aliphatic chain, and which are obtained by condensing the suitable amine with *acrylonitrile arid hydrogenating to the corresponding diamine. Commercially available aliphatic polyamines of this type are those marketed by Armour and Company as Duo meens, which are prepared by the condensation of a dodecyl (coco) amine or an octadecyl (tallow) amine with acrylonitrile followed by hydrogenation to the corresponding diamine product; these products are marketed as Duomeen C and Duorneen T, respectively.
The diflucro-boric acid, a liquid, may be conveniently prepared by reacting B 0 with hydrogen fluoride as taught by F. 5. Sowa et al, EACS 57,454 (1935).
The hydrolyzed phosphorus sulfide-hydrocarbon reaction product may be prepared by any method known to the prior art. We prefer to react a hy'clrocanbon with from about 1% to about 50%, and preferably from about 5% to about 25% of phosphorus sulfide at a temperature of from about 290 F. to about 600 F. in a non-oxidizing atmosphere, as, for example, in a nitrogen atmosphere. The reaction is carried out for from about one to about ten hours or more, and preferably for about five h-curs. The reaction may be carried out in the presence of a sulfurizing agent such as sulfur, sulfur chlorides, etc, if desired. The product is hydrolyzed rat a temperature of from about 200 F. to about 500 F, and preferably at a temperature of from about 220 F. to about 400 F. by hydrolyzing means, for example, by introducing steam through the reaction mixture. The hydrolyzed product may be solvent extracted to remove salts of inorganic phosphorus acids and low molecular Weight organic phosphorus acids formed during hydrolysis. Solvent extraction may be accomplished in accordance with the method described by Norman E. Le-mrnon et al. in US. 2,843,579, issued July 15, 1958.
in the phosphorus sulfide-hydrocarbon reaction used for preparing starting materials for the additive compositions of the present invention, any phosphorus sulfides such as as, P 3 P 3 or other phosphorus sulfides and preferably phosphorus pentasulfide, P 8 may be reacted with a hydrocarbon.
The hydrocarbons used in the phosphorus sulfidehydrocarbon reaction may be polymers such as monoolefin polymers, copolymers, graft polymers, etc. and may also be unpolymerized or unpolymerizable hydrocarbons such as olefins, parafiins, cycloparailins, aromatic hydrocarbons, etc.
The mono-olefin polymer to be treated may' be the polymer resulting from the polymerization of low molecular weight mono-olefins preferably the isomonoolefins, such as iso'butylene and isoarnylene and/ or the copolymers obtained by the polymerization of hydrocarbon mixtures containing isomono-olefins and mono-olefins of less than six carbon atoms and preferably those of four carbon atoms. The polymer may be obtained by the polymerization of these olefins or mixed olefins in the presence of catalysts such as sulfuric acid, phosphoric acid, or boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel-Crafts type. The polymers advantageously have molecular weights ranging from about 150 to about 50,000 or more, and preferably from about 500 to about 10,000.
Various polymerized starting materials prepared by methods well known in the art may be used. For example, as a starting material there can be used the polymer or synthetic lubricating oil obtained by polymerizing the unsaturated hydrocarbons resulting from the vapor phase cracking of paraffin waxes in the presence of aluminum chloride which is fully described in US. Patents Nos. 1,955,260; 1,970,402; and 2,091,398. Still another type of olefin polymer which may be employed is the polymer resulting from the treatment of vapor phase cracked gasoline and/ or gasoline fractions with sulfuric acid or solid adsorbents, such as fullers earth, whereby the unsaturated polymerized hydrocarbons are removed. Also contemplated within the scope of this invention is the treatment with phosphorous sulfide of the polymers resulting from the voltolization of hydrocarbons as described for example in US. Patents Nos. 2,197,768 and 2,191,787.
Other hydrocarbons which we can use as reactants in the preparation of the phosphorus sulfide reaction prod not are parafijns, olefins, aromatics or alkyl aromatics, cyclic aliphatics, petroleum fractions, such as lubricating oil fractions, petrolatums, waxes, cracking cycle stocks, condensation products of the foregoing hydrocarbons, solvent extracts of petroleum extracts, etc.
The parafi'in hydrocarbons can be those obtained from petroleum oils such as bright stock residuums, lubricating oil distillates, petrolatums, or parafiin waxes. We may also halogenate any of the foregoing paraflins and condense the same with aromatic hydrocarbons in the presence of anhydrous inorganic halides such as aluminum chloride, zinc chloride, boron fluoride and the like.
An examples of high molecular weight olefinic hydrocarbons which we may employ as reactants are cetene (C cerotene (C melene (C and mixed high molecular weight algenes obtained by cracking petroleum oils.
Other preferred olefins suitable for the preparation of the herein described phosphorus sulfide reaction products are olefins having at least carbon atoms in the molecular of which from about 13 carbon atoms to about 18 carbon atoms, and preferably at least 15 carbon atoms in a long chain. Such olefins can be obtained by the dehydrogenation of paraffins, such as by the cracking of paraffin waxes or by the dehalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated parafiin waxes.
As further examples of starting materials for the preparation of the hydrolyzed phosphorous sulfide-hydrocarbon, any of the hydrocarbons recited as useable by Norman E. Lemmon et al. in US. 2,843,579, issued July 15, 1958, may be employed herein.
More particularly, the additive composition concentrates of our present invention are formed by neutralizing a hydrolyzed phosphorus sulfide-hydrocarbon reaction product, formed, for example, as indicated above and preferably solvent extracted, with an amine compound having 2 or more carbon atoms and preferably an aliphatic polyamine as defined above. The neutralized product is then reacted with difiuoroboric acid preferably in amounts corresponding to from about 1 to about 3 moles boron per mole of neutralized product. We
add up to about 1.1 moles of amine compound per mole of acid phosphorous in the hydrolyzed reaction product depending on the type of amine compound used. It is preferred to neutralize only one amine group of a given amine compound and, therefore, from about 1 to about 1.1 moles of the amine compound per mole of acid phosphorus is preferred. No solvent is necessary for the reaction since difiuoroooric acid is a liquid which is sufficiently soluble in the reaction mixture. During the difluoroboric acid reaction, it may be advantageous to stir the mixture of neutralized reaction product and difiuoroboric acid and to warm the mixture for a short period of time, for example about one hour, to increase the solubility of the difluoroboric acid. The reaction mixture is then heated to a temperature above C. to strip off water and allow the reaction to go to completion. We have found that when water is not stripped 01f the reaction is reversible and will not go to completion due to the instability of the reaction product in the presence of water. During Warming, the reaction mixture should not be heated to a temperature at which the amine is driven from the mixture. If temperatures higher than the boiling point of the amine are used means for retaining the amine, such as, for example, refluxing, should be employed. An alternative method of forming the fluorine and boron-containing amine-neutralized reaction products which we have found acceptable is by first reacting the difiuoroboric acid with the amine compound and then reacting the resulting product with the phosphorus sulfide-hydrocarbon reaction product.
If the product should be hazy due to the presence of impurities, for example the presence of excess difluoroboric acid which has not reacted with the neutralized phosphorus sulfide hydrocarbon reaction product or has not dissolved therein, it may be desirable to filter the product through diatomaceous earth to obtain a suitably clear product. The products formed in the above boron reaction contain chemically bonded boron and fluorine.
The additive composition, prepared in accordance with the preferred method set out above, may be used in lubricating oils in varying amounts constituting minor proportions of the total lubricating composition. The amount of additive used should be in excess of 0.1 weight percent. The additive is efiective in imparting improved detergency lubricating oils even when used in such small amounts as range from about 0.1 weight percent. However, it is preferred to add the additive composition to the lubricating oil in amounts of from about one weight percent to about 10 weight percent although much greater amounts even above 15 Weight percent may be advantageously employed. The additive when used in a lubricating oil in an internal combustion engine was also found to suppress the octane requirement increase of the engine probably by entering the combustion chamber by the process of blow-by.
HYDROLYZED INTERMEDIATE A hydrolyzed phosphorus sulfide-hydrocarbon reaction product is prepared by reacting about 15.5 wt. percent P S with a butylene polymer having a molecular weight of about 750-800 at a temperature of about 450 F. in a nitrogen atmosphere. The reaction is continued for about five hours for product formation. The product has a phosphorus content of about 4.3% and a sulfur content of about 7.5%. The reaction product formed is then hydrolyzed with steam at a temperature of about 300 F. to about 400 F. The hydrolyzed product was diluted, for ease of handling, to about a 60% concentrate with a solvent extracted Mid-Continent 5W mineral oil having a viscosity of about 38 SSU at 210 F. The product was then contacted with clay (fullers earth) and filtered to remove inorganic impurities. The resulting clay treated product was used as a starting material for the preparation of additives in subsequent examples.
As a specific embodiment of our invention, the following examples are given by way of illustration and are not intended as limitations to the invention.
Example I 2030 grams (1.24 moles) of the clay contacted hydrolyzed intermediate Were reacted with 141 grams (L36 moles, 1.1 moles per mole of intermediate) of diethylenetriamine and a basic salt was formed. The basic salt was treated with 253 grams (3 moles) of difiuoroboric acid (E B- 13.1 159 C.) with stirring at 100 C. for four hours and 1320 grams of solvent extracted Mid- Continent 5W mineral oil having a viscosity of about 38 SSU at 210 F. were then added. The reaction mixture was filtered through Celite. The filtrate was a bright, brown, oil-soluble product which had a boron content of 0.35 wt. percent, a nitrogen content of 1.35 wt. percent, a phosphorus content of 1.16 wt. percent and a fluorine content of 2.0 wt. percent.
Example 11 2035 grams (1.24 moles) of the clay contacted hydrolyzed intermediate were reacted with 199 grams (1.36 moles, 1.1 moles per mole of intermediate) of triethylenetetramine and a basic salt was formed. The basic salt was treated with 296 grams (3.53 moles) of difiuoroboric acid (H BO F B.-P. 159 C.) with stirring at 100 C. for four hours and 1059 grams of solvent extracted Mid-Continent 5W mineral oil having a viscosity of about 38 SSU at 210 F were then added. The reaction mixture was blown with nitrogen at 125 F. and zfiltered through Celite. The filtrate was a bright, brown, oil-soluble product which had a boron content of 0.78 wt. percent, a nitrogen content of 1.77 wt. percent, a phosphorus content of 1.23 wt. percent and a fluorine content of 2.7 wt. percent.
Example 111 2000 grams (1.22 moles) of the clay contacted hydrolyzed intenmediate were reacted with 537 grams (1.34 moles, 1.1 moles per mole of intermediate) or" Duomeen T and a basic salt was formed. Duomeen T commercially prepared by Armour Chemical Division, Chicago, Illinois, is predominantly a propylene diarnine having a side chain derived from tallow-fatty acid and melting in the range of from about 44 C. to about 48 C.; the side chain is attached directly to the one nitrogen atom. The basic salt was treated with 125 grams (1.49 moles) of difluoroboric acid (H BO F 13.1. 159 C.) with stirring at 100 C. for four hours and the reactants were then diluted with solvent extracted Mid Continent 5W mineral oil having a viscosity of about 38 SSU at 210 F. and filtered through Celite. The filtrate was a bright, brown, oil-soluble product which had a boron content of 0.66 wt. percent, a nitrogen content of 1.02 wt. percent, a phosphorus content of 1.62 wt. percent and a fluorine content of 0.92 wt. percent.
The eifectivcness of the products of the present invention in improving the detergency characteristics of lubricating oils is demonstrated by the data in Table I. The data were obtained by subjecting a commercial-type lubricating oil with and without the product of the above example to the detergency and oxidation test known as the Squalene Indiana Stirring Oxidation Test (1.8.0.11). In the Squalene I.S.O.T., by weight of squalene (a highly unsaturated reactive hydrocarbon that polymerizes easily and forms a tightly adhering varnish during the test) is added to the oil to be tested and the mixture is heated at 300 F. in a 500- cc. glass beaker in the preserrce of 5 square inches of copper and 10 square inches of iron. Four glass rods of 6 mm. diameter are suspended in the oil which is stirred at about 1300 r.p.m. by means of a glass stirrer. After 72 hours the test is ended and varnish values are determined. Varnish values or ratings are based upon visual inspection of the glass rods, in which a rod free of any varnish deposit is given a rating of 10 while a badly coated rod is. given a rating of 1. Rods having appearances between these extremes are given intermediate values. The following comparative samples were subjected to the Squalene I.S.O.T. with the results listed in Table I.
TABLE I Sample: Varru'sh rating A 4 to 5 A composition of the present invention was comparatively subjected to a Detergency Screening Test which rates detergency by a determination of piston varnish deposits. The test was carried out in a current model Chevrolet Powerglide Engine operating for one hour at 500 r.p.m. and no load and for 6 subsequent hours at 2500 rpm. and a load of 3.1-1.1. The oil temperature for the first hour was F, for the second and third hours was F. and for the 4 remaining hours was 220 F. The water temperature @501 the first 3 hours was from 85 to 95 F. and for the remaining 4 hours was to 180 F. Each 7 hours so constituted is regarded a cycle. For the Detergency Screening Tests, 4 cycles were run with a 4-hour rest between each cycle. At the end of the 4 cycles, the pistons were examined for varnish and rated on a scale whereby pistons free of varnish are rated 10 and pistons having very heavy varnish are rated one. The following samples were subfiected to the above test and the comparative results are indicated in Table II.
' Sample D6.6 weight percent of a barium-containing neutralized phosphorus pentasulfide-butylene polymer (mol wt. of about 750 to 800) reaction product 1 in Sample A.
TABLE II.RESULTS 0F IgETERGENCY SCREENING 4. Ct Sample: Piston varnish rating A 5.3
As can be seen from Table Hi, the composition of the present invention indicated as Sample B gave superior piston varnish rating results in comparison with metalcontaining detengent additives as exemplified by Samples C and D when compounded in commercial-type lubricants and also gave superior results in comparison with the very low piston varnish rating of the lubricant Without any detergent additive as exemplified by Sample A.
The herein described additive compositions of the present invention can be used as indicated above in varying amounts of from 0.1 up to about 15 percent in lubri- For comparison of metal-containing phosphorus sulfidehydrocarbon reaction products with the amine-containing fluoroboric acid complexes.
cating oils. Although the present invention has been illustrated by the use of the additive compositions in mineral lubricating oils, it is not restricted thereto. Other lubricating oil bases can be used, such as hydrocarbon oils, both natural and synthetic, for example, those obtained by the polymerization of olefins, as well as synthetic lubricating oils of the alkylene oxide type and the polycarboxylic acid ester type, such as the oil soluble esters of adipic acid, sebacic acid, azelaic acid, etc. It is also contemplated that various other well known additives, such as antioxidants, anti-foaming agents, pourpoint depressors, extreme pressure agents, antiwear agents, may be incorporated in lubricating oils containing the additives of our invention.
Concentrates of a suitable oil base containing more than percent, for example up to 50 percent or more, of the additives of this invention alone or in combination with other additives can be used for blending with hydrocarbon oils or other oils in the proportions desired for the particular conditions of use to give a finished lubricating product containing the additives of this invention.
Unless otherwise stated, the percentages given herein and in the claims are percentages by weight.
Although we have described our invention by reference to specific embodiments and examples thereof, such specific embodiments and examples as have been given are merely for the purpose of illustration of the invention and are not intended as limiting its scope. It is intended that modifications and variations of the present inventions which are apparent from our foregoing description to those skilled in the art are to be considered within the scope of our present invention except as stated in the following appended claims.
V/e claim:
1. As a new composition of matter, an oil-soluble detergent neutralized reaction product prepared by the process comprising: reacting a phosphorus sulfide with a hydrocarbon; hydrolyzing the resulting phosphorus sulfidehydrocarbon reaction product; and reacting the hydrolyzed product with fluoroboric acid in an amount corresponding to from about one to about three moles of boron per mole of reaction product and an aliphatic polyamine having from 2 to 21 carbon atoms in the aliphatic group in an amount corresponding to from about one to about 1.1 moles of polyamine per mole of acid phosphorus, at a temperature below the temperature at which said polyamine is driven from the mixture of reactants.
2. A lubricating composition comprising a major amount of hydrocarbon lubricating oil and from about 0.1 to about weight percent of the composition of claim 1.
3. The composition of claim 1 wherein the aliphatic polyamine is diethylenetriamine.
4. The composition of claim 1 wherein the aliphatic polyamine is a propylene diamine having a side chain derived from taliow-fatty acid and melting in the range of 44 to 48 C.
5. The composition of claim 1 wherein the aliphatic polyamine is triethylene tetramine.
6. As a new composition of matter, an oil-soluble detergent neutralized reaction product prepared by the process comprising the steps of: reacting a phosphorus sulfide with a hydrocarbon; hydrolyzing the resultant phosphorus sulfide-hydrocarbon reaction product; neutralizing the hydrolyzed product with an aliphatic polyamine having from 2 to 21 carbon atoms in the aliphatic group in an amount corresponding to from about one to about 1.1 moles of polyamine per mole of acid phosphorus; and reacting the neutralized product with fluoroboric acid in an amount corresponding to from about one to about three moles of boron per mole of reaction product at a temperature below the temperature at which said polyamine is driven from the mixture of reactants.
7. A lubricating composition comprising a major amount of hydrocarbon lubricating oil and from about 0.1 to about 20 weight percent of the composition of claim 6.
8. As a new composition of matter, an oil-soluble de tergent neutralized reaction product prepared by the process comprising the steps of: reacting 'a phosphorus sulfide with a hydrocarbon; hydrolyzing the resultant phosphorus sulfide-hydrocarbon reaction product; reacting fluoroboric acid in an amount corresponding to from about one to about three moles of boron per mole of reaction product with an aliphatic polyamine having from 2 to 21 carbon atoms in the alkylene group and containing at least two primary amino nitrogen atoms in an amount corresponding to from about one to about 1.1 moles of polyamine per mole of acid phosphorus; and reacting the resulting reaction product with a hydrolyzed phosphorus sulfidehydrocarbon reaction product at a temperature below the temperature at which the polyamine is driven from the mixture of reactants.
9. As a new composition of matter, an oil-soluble detergent neutralized reaction product prepared by the process comprising the steps of: reacting phosphorus sulfide with a hydrocarbon; hydrolyzing the resulting phosphorus sulfide-hydrocarbon reaction product; neutralizing the resulting hydrolyzed product with from about one to about 1.1 moles of ethylene diamine per mole of hydrolyzed reaction product; and reacting the resulting neutralized product with from about one to about three moles based on boron of fluoroboric acid per mole of neutralized product at a temperature below the temperature at which the ethylene diamine is driven from the mixture of reactants.
10. As a new composition of matter, an oil-soluble detergent neutralized reaction product prepared by the process comprising the steps of: reacting phosphorus sulfide with a butene polymer at a temperature of from about 200 F. to about 600 F. hydrolyzing the resulting phosphorus sulfide-butene polymer reaction product; neutralizing the resulting hydrolyzed product with from about one to about 1.1 moles per mole of hydrolyzed reaction product of an alkylene polyamine having the formula RNH(CH NH wherein R is a C to C aliphatic chain; reacting the resulting neutralized product with from about one to about three moles based on boron of fluoroboric acid per mole of neutralized product at a temperature below the temperature at which the polyamine is driven from the mixture of reactants; and heating the reactants to a temperature above C. whereby water is stripped from the reaction mixture.
11. A lubricant additive concentrate consisting essentially of a hydrocarbon lubricating oil containing more than about 10% of an oil-soluble detergent neutralized reaction product prepared by the process comprising: reacting a phosphorus sulfide with a hydrcarbon; hydrolyzing the resulting phosphorus sulfide-hydrocarbon reaction product; and reacting the hydrolyzed product with fluoroboric acid in an amount corresponding to from about one to about three moles of boron per mole of reaction product and an aliphatic polyamine having from 2 to 21 carbon atoms in the aliphatic group in an amount corresponding to from about one to about 1.1 moles of polyamine per mole of acid phosphorus, at a temperature below the temperature at which the polyamine is driven from the mixture of reactants.
References Cited in the file of this patent UNITED STATES PATENTS 2,053,474 Graves et a1 Sept. 8, 1936 2,160,917 Shoemaker et al. June 6, 1939 2,346,156 Farrington et al. Apr. 11, 1944 2,636,858 Jones et al Apr. 28, 1953 2,798,045 Buck et al. July 2, 1957 2,809,934 Alford et a1 Oct. 15, 1957 2,900,376 Sabol et al. Aug. 18, 1959
Claims (1)
11. A LUBRICANT ADDITIVE CONCENTRATE CONSISTING ESSENTIALLY OF A HYDROCARBON LUBRICATING OIL CONTAINING MORE THAN ABOUT 10% OF AN OIL-SOLUBLE DETERGENT NEUTRALIZED REACTION PRODUCT PREPARED BY THE PROCESS COMPRISING: REACTING A PHOSPHORUS SULFIDE WITH A HYDCARBON; HYDROLYZING THE RESULTING PHOSPHORUS SULFIDE-HYDROCARBON REACTION PRODUCE; AND REACTING THE HYDROLYZED PRODUCT WITH FLUOROBORIC ACID IN AN AMOUNT CORRESPONDING TO FROM ABOUT ONE TO ABOUT THREE MOLES OF BORON PER MOLE OF REACTION PRODUCT AND AN ALIPHATIC POLYAMINE HAVING FROM 2 TO 21 CARBON ATOMS IN THE ALIPHATIC GROUP IN AN AMOUNT CORRESPONDING TO FROM ABOUT ONE TO ABOUT 1.1 MOLES OF POLYAMINE PER MOLE OF ACID PHORSPHORUS, AT A TEMPERATURE BELOW THE TEMPERATURE AT WHICH ITHE POLYAMINE IS DRIVEN FROM THE MIXTURE OF REACTANTS.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL246131D NL246131A (en) | 1958-12-08 | ||
FR812272A FR1246407A (en) | 1958-12-08 | 1958-12-07 | Lubricant additive |
US778583A US3108959A (en) | 1958-12-08 | 1958-12-08 | Lubricant additive and composition containing same |
US778606A US3089851A (en) | 1958-12-08 | 1958-12-08 | Lubricant additive and composition containing same |
US778576A US3108958A (en) | 1958-12-08 | 1958-12-08 | Lubricant additive and composition containing same |
DEST15883A DE1255221B (en) | 1958-12-08 | 1959-12-08 | Lubricating oil |
GB41612/59A GB930504A (en) | 1958-12-08 | 1959-12-08 | Boron and nitrogen-containing phosphor-sulphurized products, their preparation and their use as lubricant additives |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US778583A US3108959A (en) | 1958-12-08 | 1958-12-08 | Lubricant additive and composition containing same |
US778606A US3089851A (en) | 1958-12-08 | 1958-12-08 | Lubricant additive and composition containing same |
US778576A US3108958A (en) | 1958-12-08 | 1958-12-08 | Lubricant additive and composition containing same |
Publications (1)
Publication Number | Publication Date |
---|---|
US3108958A true US3108958A (en) | 1963-10-29 |
Family
ID=27419742
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US778576A Expired - Lifetime US3108958A (en) | 1958-12-08 | 1958-12-08 | Lubricant additive and composition containing same |
US778583A Expired - Lifetime US3108959A (en) | 1958-12-08 | 1958-12-08 | Lubricant additive and composition containing same |
US778606A Expired - Lifetime US3089851A (en) | 1958-12-08 | 1958-12-08 | Lubricant additive and composition containing same |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US778583A Expired - Lifetime US3108959A (en) | 1958-12-08 | 1958-12-08 | Lubricant additive and composition containing same |
US778606A Expired - Lifetime US3089851A (en) | 1958-12-08 | 1958-12-08 | Lubricant additive and composition containing same |
Country Status (5)
Country | Link |
---|---|
US (3) | US3108958A (en) |
DE (1) | DE1255221B (en) |
FR (1) | FR1246407A (en) |
GB (1) | GB930504A (en) |
NL (1) | NL246131A (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3185728A (en) * | 1960-06-20 | 1965-05-25 | Texaco Inc | Ethylene diamine salts of thiophosphonic acids |
US3294684A (en) * | 1963-07-11 | 1966-12-27 | Standard Oil Co | Lubricant compositions containing detergency additives |
US4438013A (en) | 1983-05-27 | 1984-03-20 | Olin Corporation | Phosphorylated and thiophosphorylated poly(oxyalkylated) hydrazines and selected adducts and their use as corrosion inhibitors |
US5026493A (en) * | 1989-08-03 | 1991-06-25 | Ethyl Petroleum Additives, Inc. | Reduced ash content lubricants |
US5652201A (en) * | 1991-05-29 | 1997-07-29 | Ethyl Petroleum Additives Inc. | Lubricating oil compositions and concentrates and the use thereof |
CN115820329B (en) * | 2022-12-30 | 2023-10-31 | 太原理工大学 | Lubricating oil with lamellar borophosphate amine compound as additive and preparation method thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2053474A (en) * | 1934-12-11 | 1936-09-08 | Du Pont | Higher alkyl borates and silicates and process for preparing same |
US2160917A (en) * | 1937-06-10 | 1939-06-06 | Standard Oil Co | Lubricant |
US2346156A (en) * | 1942-02-16 | 1944-04-11 | Standard Oil Co | Compounded lubricant |
US2636858A (en) * | 1951-06-07 | 1953-04-28 | Standard Oil Dev Co | Mineral oil additive |
US2798045A (en) * | 1954-09-27 | 1957-07-02 | Shell Dev | Lubricating compositions |
US2809934A (en) * | 1953-10-01 | 1957-10-15 | Standard Oil Co | Detergent lubricants and lubricating oil additives and process of making the same |
US2900376A (en) * | 1955-10-31 | 1959-08-18 | Standard Oil Co | Hydrolysis of phosphorus sulfide-hydrocarbon reaction product |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2316082A (en) * | 1941-03-24 | 1943-04-06 | Standard Oil Co | Lubricant |
US2636258A (en) * | 1949-02-23 | 1953-04-28 | Jones Allen | Fluid can punch and opener |
BE581744A (en) * | 1950-12-22 | |||
US3002924A (en) * | 1958-05-26 | 1961-10-03 | Standard Oil Co | Lubricant additive and composition containing same |
-
0
- NL NL246131D patent/NL246131A/xx unknown
-
1958
- 1958-12-07 FR FR812272A patent/FR1246407A/en not_active Expired
- 1958-12-08 US US778576A patent/US3108958A/en not_active Expired - Lifetime
- 1958-12-08 US US778583A patent/US3108959A/en not_active Expired - Lifetime
- 1958-12-08 US US778606A patent/US3089851A/en not_active Expired - Lifetime
-
1959
- 1959-12-08 DE DEST15883A patent/DE1255221B/en active Pending
- 1959-12-08 GB GB41612/59A patent/GB930504A/en not_active Expired
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2053474A (en) * | 1934-12-11 | 1936-09-08 | Du Pont | Higher alkyl borates and silicates and process for preparing same |
US2160917A (en) * | 1937-06-10 | 1939-06-06 | Standard Oil Co | Lubricant |
US2346156A (en) * | 1942-02-16 | 1944-04-11 | Standard Oil Co | Compounded lubricant |
US2636858A (en) * | 1951-06-07 | 1953-04-28 | Standard Oil Dev Co | Mineral oil additive |
US2809934A (en) * | 1953-10-01 | 1957-10-15 | Standard Oil Co | Detergent lubricants and lubricating oil additives and process of making the same |
US2798045A (en) * | 1954-09-27 | 1957-07-02 | Shell Dev | Lubricating compositions |
US2900376A (en) * | 1955-10-31 | 1959-08-18 | Standard Oil Co | Hydrolysis of phosphorus sulfide-hydrocarbon reaction product |
Also Published As
Publication number | Publication date |
---|---|
FR1246407A (en) | 1960-10-10 |
DE1255221B (en) | 1967-11-30 |
GB930504A (en) | 1963-07-03 |
NL246131A (en) | |
US3089851A (en) | 1963-05-14 |
US3108959A (en) | 1963-10-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2316082A (en) | Lubricant | |
US2910439A (en) | Corrosion inhibited compositions | |
US3131150A (en) | Lubricating oil compositions containing n-substituted alkenyl succinimides in combination with polyamines | |
US3275554A (en) | Polyolefin substituted polyamines and lubricants containing them | |
US2760933A (en) | Lubricants | |
US3779928A (en) | Automatic transmission fluid | |
US3361673A (en) | Lubricating oil compositions containing alkenyl succinimides of tetraethylene pentamine | |
US3288714A (en) | Lubricating oil compositions containing alkenyl succinic anhydrides | |
US2638450A (en) | Reaction products of nu-alkylated polyalkylenepolyamines and alkenyl succinic acid anhydrides | |
US2830019A (en) | Additive for mineral oil | |
US3185645A (en) | Oxidation inhibited lubricants | |
US4056531A (en) | Polymonoolefin quaternary ammonium salts of triethylenediamine | |
US2367468A (en) | Lubricants | |
US2316088A (en) | Lubricant | |
GB1573872A (en) | Alkenylamines and their application as additives for lubricating oils and fuels | |
US4108858A (en) | Polyolefin quaternary pyridinium salts | |
CA1038851A (en) | Dispersant-detergent libricant and fuel additives | |
US3108958A (en) | Lubricant additive and composition containing same | |
US2316078A (en) | Lubricant | |
US4094802A (en) | Novel lubricant additives | |
KR930011072B1 (en) | Detergent, dispersant and anti-rust additive for fuels and lubricating oil | |
US2507731A (en) | Process of reacting phosphorus sulfide and olefinic hydrocarbon | |
US3247110A (en) | Fuel oil and lubricating oil compositions containing metal salts of the mono-amidesof tetrapropenyl succinic acid | |
US2316083A (en) | Lubricant | |
US3412029A (en) | Organic compositions |