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
  • C10M159/18—Complexes with metals
• • 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 Table
  • C07F9/02—Phosphorus compounds
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  • 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 Table
  • C07F9/02—Phosphorus compounds
  • C07F9/04—Reaction products of phosphorus sulfur compounds with hydrocarbons
• • 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
  • 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
  • C10M2209/082—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 monocarboxylic
• • 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
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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
  • 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
  • C10M2227/061—Esters derived from boron
• • 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
  • C10N2010/02—Groups 1 or 11
• • 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 novel compositions of matter which are effective as multi-function addition agents in lubricant compositions. More particularly, this invention pertains to improved lubricant compositions containing novel oil-soluble barium-containing neutralized phosphorus sulfide-hydrocarbon reactions having the ability to improve detergency properties of a lubricating oil.
• Lubricating oils employed in internal combustion engines such as spark ignition and diesel engines generally. require the use of more than one addition agent to improve the serviceability of the lubricating oil under the conditions of operation of the engine.
• many different types of additives are employed.
• Such addition agents have the property of maintaining clean engines and are referred to as detergent type addition agents.
• type addition agents generally must be eltective under heavy duty, high temperature conditions of engine opera.- tion. It is desirable to provide detergency addition agents for such conditions.
• the addition agents of this invention are easily filtered and clear in appearance and are useful as multi-purpose addition agents in lubricating oils in amounts from about .002 to about 25 weight percent for the purpose of imparting detergency to the lubricating oil.
• the addition agents of this invention Further, modern 1 are also effective in imparting rust inhibition properties to the lubricating oil.
• the process for preparation of the reaction product complexes eliminates hazy appearance in the final product.
• the additive complexes of this invention are formed by neutralizing a hydrolyzed phosphorus sulfide-hydrocarbon reaction product with an excess of an inorganic basic alkali metal or alkaline earth metal compound in the presence of boric acid and a polymerized fatty acid, i.e., a polymerization product of an unsaturated fatty acid.
• the neutralization is carried out using an alcohol-containing reaction solvent for the neutralization reaction mixture.
• the basic neutralization reagent i.e., the inorganic basic alkali metal or alkaline earth metal compound
• the inorganic basic alkali metal or alkaline earth metal compound will hereinafter be referred to for convenience as inorganic basic compound.
• the inorganic basic compound is an oxide, hydroxide, carbonate, sulfide, or the like of lithium, sodium, potassium, calcium, barium, strontium, etc.
• Examples are barium oxide, barium sulfide, barium carbonate, calcium carbonate, calcium oxide, calcium sulfide, potassium hydroxide, sodium bicarbonate, sodium sulfide, sodium hydroxide, lithium hydroxide, lithium sulfide, strontium oxide, etc. Barium oxide is particularly preferred.
• the alcohol reaction solvent may be any aliphatic alcohol boiling below about 350 F. or mixture of Such alcohol with water. More advantageously the aliphatic alcohol is a saturated aliphatic alcohol having from 1 to about 7 carbon atoms. Methanol is particularly preferred. Where a mixture of alcohol and water is used ;-methanol, ethanol, isopropanol, butanol, pentenol, pentanol, methyl-butyl alcohol, hexanol, hexenol, cyclohex- .-anol,-ethylhexyl alcohol, cetyl alcohol, and the like.
• the alcohol reaction solvent i used during the above neutralization reaction with excess inorganic basic compound in amounts sufiicient to provide from about 2 to about 15 mols of aliphatic alcohol per mol of inorganic basic compound and preferably from about 3 to about 7 mols per mol of inorganic basic compound.
• the neutralization is carried out by reacting the inorganic basic compound, the hydrolyzed phosphorus sulfide-hydrocarbon reaction product, boric acid, and the polymerized fatty acid in admixture at a temperature in a range from about F. to about 400 F. and preferably from about F. to about 200 F. It is advantageous to carry the reaction out at or below the reflux temperature of the alcohol-containing reaction solvent since the reaction temperature can thereby be more easily controlled.
• the neutralization with the inorganic basic compound forms a neutralized product having a high ratio of alkali metal or alkaline earth metal to phosphorus.
• the inorganic basic compound is added to the reaction mixture as a slurry in a diluent mineral oil or water or other diluent.
• the neutralization reaction is carried out in the presence of the alcohol-containing reaction solvent, the boric acid, and the polymerized fatty acid until neutralization is complete.
• the resulting product is filtered to remove solid materials such as unreacted inorganic basic compound or inorganic salts thereof; filtration may be easily accomplished by diluting the product with a mineral lubricating oil and heating the diluted product to a temperature in the range of from about 200 to about 400 F. and preferably about 350 F. and then filtering the heated diluted product through an absorbent material such as silica gel, Celite, Attapulgus clay, fullers earth, and the like.
• the alcohol-containing reaction solvent, the boric acid, and the polymerized fatty acid are heated to reaction temperature before addition of the inorganic basic compound for neutralization.
• the hydrolyzed phosphorus sulfide-hydrocarbon reaction product should not be permitted to react substantially with the inorganic )basic compound before addition of the boric acid and polymerized fatty acid.
• the boric and polymerized acids are added before the inorganic basic compound or alternatively after or at the same time as the inorganic basic compound but before the reaction mixture is heated to reaction temperature.
• the hydrolyzed phosphorus sulfide-hydrocarbon reaction product may be prepared by reacting a normally liquid hydrocarbon with a phosphorus sulfide, such as P S P 5 P 8 or other phosphorus sulfides, and prefer- ;ably phosphorus pentasulfide, P 8 and hydrolyzing the resulting product.
• a normally liquid hydrocarbon constituent of this reaction is suitably a high boiling hydrocarbon such as is described in detail in U.S. 2,316,080, 2,316,082, and 2,316,088, each issued to Loane et al. on April 6, 1943.
• hydrocarbon constituent of this reaction can be any of the type hereinafter described, it is preferably a mono-olefin hydrocarbon polymer resulting from the polymerization of low molecular weight mono-olefinic hydrocarbons or isomono-olefinic hydrocarbons, such as vbutylenes, or the copolymers obtained by the polymerization of hydrocarbon mixtures containing isomono-olefins and mono-olefins or mixtures of olefins in the presence of a catalyst, such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel-C-rafts type.
• a catalyst such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel-C-rafts type.
• the polymers employed are preferably mono-olefin polymers or mixtures of mono-olefin polymers and isomono-olefin polymers having molecular weights ranging from about 1-50 to about 50,000 or more, and preferably from about 300 to about 10,000.
• Such polymers can be obtained, for example, by the polymerization in the liquid phase of a hydrocarbon mixture containing mono-olefins and isomono-olefins such as butylene and isobutylene at a temperature of from about -80 F. to about 100 F. in the presence of a metal halide catalyst of the Friedel-Crafts types such as, for example, boron fluoride, aluminum chloride, and the like.
• Essentially parafiinic hydrocarbons such as bright stock residuums, lubricating oil distillates, petrolatums, or par- -afiin waxes, may be used.
• condensation products of any of the foregoing hydrocarbons uusally through first halogenating the hydrocarbons, with aromatic hydrocarbons in the presence of anhydrous inorganic halides, such as aluminum chloride, zinc chloride, boron fluoride, and the like.
• olefins suitable for the preparation of the herein described phosphorus sulfide reaction products are olefins having at least 20 carbon atoms in the molecule of which from about 13 carbon atoms to about 18 carbon atoms, and preferably at least 15 carbon atoms, are in a long chain.
• Such olefins can be obtained by the dehydrogenation of paraflins, such as by the cracking of paraffin waxes or by the dehalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated paraffin waxes.
• the phosphorus sulfide-hydrocarbon reaction product is prepared by reacting the phosphorus sulfide, e.g. P 8 with the hydrocarbon at a temperature of from about 200 F. to about 600 F., preferably from about 300 F. to about 500 F., using from 1% to about 50%, preferably from about 5% to about 25% of phosphorus sulfide; the reaction is carried out in from about one to about ten hours. It is preferable to use an amount of the phosphorus sulfide that will completely react with the hydrocarbon so that no further purification is necessary; however, an excess of the phosphorus sulfide can be used, and the unreacted material separated by filtration.
• the reaction if desired, can be carried out in the presence of a sulfurizing agent such as sulfur or a halide of sulfur as described in U.S. 2,316,087, issued to J. W. Gaynor et al. April 6, 1943. It is advantageous to maintain a non-oxidizing atmosphere, for example an atmosphere of nitrogen, in the reaction vessel.
• a sulfurizing agent such as sulfur or a halide of sulfur as described in U.S. 2,316,087, issued to J. W. Gaynor et al. April 6, 1943.
• a non-oxidizing atmosphere for example an atmosphere of nitrogen
• the hydrolyzed product, containing inorganicphosphorus acids formed during the hydrolysis can be used as such in the subsequent neutralization stage; or it can be substantially freed of the inorganic phosphorus acids by contacting with an adsorbent material such as Attapulgus clay, fullers earth and the like at a temperature of F.-500 F. as fully described and claimed in U.S. 2,688,412, issued to R. Watson on September 7, 1954, or by extraction with phenol or an alkanol of l to 5 carbon atoms in admixture with water as described andiclaimed in U.S. 2,843,579, issued to N. E. Lammon et al. on July 15, 1958.
• an adsorbent material such as Attapulgus clay, fullers earth and the like at a temperature of F.-500 F. as fully described and claimed in U.S. 2,688,412, issued to R. Watson on September 7, 1954, or by extraction with phenol or an alkanol of l to 5 carbon atoms in
• the bo-ric acid is used in the neutralization reaction mixture in amounts of from about 0.1 to about 5.0 moles and preferably from about 0.5 to about 2.5 mols per mol of phosphorus in the phosphorus sulfide-hydrocarbon reaction product.
• the boric acid may be added as boric acid or may be prepared in situ in the reaction mixture by adding boric acid anhydride or a boric acid ester which is capable of decomposition to give boric acid in the reaction mixture, for example, by dissociation upon heating or by dissociation through hydrolysis or other means.
• the polymerized fatty acid may be used in the neutralization reaction mixture in amounts in the range of 0.1 to 10.0 mols, and preferably 0.2 to 6.0 mols, per mol of phosphorus in the hydrolyzed phosphorus sulfidehydrocarbon reaction product.
• the polymerized fatty acids preferably are oil soluble and have a molecular weight in the range of from about 300 to about 2000.
• the polymerized fatty acids or polymerization products of the unsaturated fatty acids are those such as may be obtained by the polymerization of natural or synthetic mono-carboxylic acids which generally will have 16 to 26 carbon atoms, most frequently 18 carbon atoms, but if synthetic unsaturated fatty acids are used they may have a lesser or greater number of carbon atoms.
• the natural fatty acids are those such as linoleic, linolenic, ricinoleic (which upon heating forms linoleic acid), linoleaidic elaido-linolenic, eleostearic, arachidonic, eicosatrienoic, cetoleic, docosatrienoic and the like.
• the free fatty acids can be polymerized either thermally or with the assistance of catalysts.
• a method of thermally polymerizing free fatty acids (see U.S. 2,482,761) consists of hydrolyzing a fat or an oil, adding a small portion of water, and heating in a pressure vessel until substan-tially all of the diand tri-unsaturated fatty acids present polymerize. The resultant product is then heated ata reduced pressure to distill off vaporizable constituents, leaving behind the polymerized unsaturated fatty acids.
• the polymerization reaction is carried out at a temperature of about 300 to 360 C. for about 3 to 8 hours at a pressure varying between 75 and 500 p.s.i.g.
• the polymerization product may consist of monomers, dimers, trimers, and higher polymers of the unsaturated fatty acids.
• the various fats or oils which may be hydrolyzed to produce the free fatty acids used in the above thermal polymerization are those such as sardine oil, linseed oil, soybean oil, castor oil, peanut oil, palm oil, olive oil, cottonseed oil, sunflower seed oil, and the like.
• Another method of preparing the polymerized fatty acids consists of subjecting fats and oils such as have been listed supra (without previous hydolysis) to a thermal or catalytic polymerization to cause polymerization of the esters of the unsaturated carboxylic acids to the dimers, trimers, and higher polymerization products thereof followed by hydrolysis to yield the corresponding polymers of the acids.
• a large source of the polymerized unsaturated fatty acids are those residual acids obtained by methanolysis (see U.S. 2,450,940) of the semidrying or drying type oils such as castor oil, soybean oil, and others listed supra, polymerizing the methyl esters, removing unpolymerized compounds, saponifying the residual esters and freeing polymerized acids therefrom.
• the products of catalytic polymerization of semi-drying oils such as the BF polymerization products of soybean oil, cottonseed oil, or the like also product polymers suitable for'use in the invention.
• polymerized unsaturated fatty acids may be used, they do not all provide the same effect, and indeed there may be pronounced differences, when used in the composition of this invention.
• a highly preferred source of the polymerized unsaturated fatty acids is obtained as a by-product still residue in the manufacture of sebacic acid by the dry distillation of castor oil in the presence of sodium hydroxide.
• a method of obtaining such by-product still residues in the. manumacture of sebacic acid is described in US. 2,470,849, isued to W. E. Hanson May 24, 1949.
• the mixture of high molecular weight unsaturated fatty acids comprises monomer, dimer, trimer and higher polymers in the ratio of from about 45% to about 55 of a monomer and dimer fraction having a molecular weight in the range of: from about 300 to 600 and from about 4.5% to about 55% of a trimers and higher polymer fraction having a molecular weight in excess of 600.
• the fatty. acid polymers result in part from a thermal polymerization. of fatty acid type constituents of the castor oil, and in part from other reactions such as the intermolecularesterification of such acid to form high molecular weight products.
• the acid mixture which is mainly a mixture of polymeric long chain polybasic carboxylic acids, is further characterized by the following specifications:
• The. polymerization products of the unsaturated fatty acids may have a molecular weight between about 400 and 2000. Those polymers having a molecular weight higher than about 500, and especially those having molecular weight averaging about 800 or higher are. particularly preferred for use in this invention.
• the polymerization products may consist primarily of dimers and trimers of linoleic acid, for example Emery 955 dimer acid which contains of the dimer, 12% of the trimer, and 3% of the monomer of linoleic acid may be used.
• Especially preferred polymerized unsaturated acids are the polymerization products of acids such as linoleic acid having a molecular Weight between about 300 and 2000, wherein the polymerization products consist of from about 45 to about 55% of monomer and dimer fraction of linoleic acid having a molecular weight ranging from 300 to 600 and from about 45% to about 55% of the trimer and higher molecular weight polymers fraction of linoleic acid having a molecular weight in excess of about 600.
• acids such as linoleic acid having a molecular Weight between about 300 and 2000
• the polymerization products consist of from about 45 to about 55% of monomer and dimer fraction of linoleic acid having a molecular weight ranging from 300 to 600 and from about 45% to about 55% of the trimer and higher molecular weight polymers fraction of linoleic acid having a molecular weight in excess of about 600.
• Example I 1220 grams of the diluted hydrolyzed phosphorous sulfide-polybutene reaction product of the above preparation, 75 grams of Har-desty D-50. Acids (described above), 300 grams of solvent extracted SAE5 mineral lubricating oil and 62 grams of boric acid were mixed with 700 cc. of methanol and 36 cc. of water. Theresulting mixture was heated at -F. for 2 hours. An oil slurry of 400 grams of barium oxide in 480 grams solvent extracted SAE-S mineral lubricating oil was then added and the reaction mixture was heated at 160 F. for 2 hours. The temperature was then increased to 350 F. and the product was filtered. The filtered product contained 13.1% barium, 1.33% phosphorous, and 0.35% boron and was clear and bright in appearance.
• Example 111 1220 grams of the diluted hydrolyzed phosphorus sulfide-polybutene reaction product of the above preparation, 12 grams of Hardesty D-SO Acids (described 7 above), 300 grams of solvent extracted SAE- mineral lubricating oil and 62 grams of boric acid were mixed with 700 cc. of methanol and 36 cc. of water. The resulting mixture was heated at 160 F. for 2 hours. An oil slurry of 400 grams of barium oxide in 480 grams solvent extracted SAE-S mineral lubricating oil was then added and the reaction mixture was heated at 160 F. for 2 hours. The temperature was then increased to 350 F. and the product was filtered. The product filtered readily and was bright and clear in appearance. The filtered product contained 12.76% barium, 1.28% phosphorus and 0.34% boron.
• Example IV A hydrolyzed phosphorus pentasulfide-polybutene reaction product was prepared in accordance with the preparation above but was diluted only to a concentration of one mol of phosphorus in 930 grams.
• 930 grams of the diluted product, 470 grams of solvent extracted SAE-S mineral lubricating oil, 70 grams of boric acid, and 75 grams of Hardesty D-50 Acids (described above) were mixed with 700 cc. methanol and 35 cc. water and heated at 160 F. (methanol reflux temperature) for about 2 hours.
• the mixture was then mixed with an oil slurry of 420 grams of barium oxide in 500 grams of solvent extracted SAE-S mineral lubricating oil and the mixture was heated for 2 hours at 160 F. After 2 hours the temperature was increased to 350 F. and the product was filtered through Celite.
• the filtered product contained 13.92% barium, 1.24% phosphorus and 0.34% boron and was clear and bright in appearance.
• compositions of this invention as addition agents in a lubricating oil was tested in accordance with the procedure of the L-l test, having CRC designation L1545 as fully described in CRC handbook, 1956 edition, Co-ordinating Research Step, New York. Briefly, the test is conducted in a lA-Sl single cylinder Caterpillar engine operating at 1000 r.p.m. at a load of 19.8 B.H.P. Within an oil temperature of 145 to 150 F. and a water jacket outlet temperature of about 175 to 180 F. The test was run for 480 hours with inspections at the end of 240, and 480 hour periods for carbon in the ring grooves, expressed in terms of percent filling of the top ring groove with carbon.
• the sample tested was formulated by adding 2.8% of the product prepared in Example IV to an SAE-30 mineral lubricating oil containing 1% of zinc dialkyl dithiophosphate and a polyisobutylene polymer viscosity index improver and having a viscosity index of about 62 sec. at 210 F.
• the results of the L-1 test are reported below. More than 25% filling of the first ring groove is considered failing.
• 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 viscosity index improvers, anti-foaming agents, pourpoint depressors, extreme pressure agents, and the like, may be incorporated in lubricating oils containing the additives of our invention.
• Concentrates of a suitable oil base containing more than 15 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 normally liquid lubricating 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 normally liquid hydrocarbon with from about 1% to about 50% of a phosphorus sulfide at a temperature in the range of from about 200 F. to about 600 F., hydrolyzing the resulting reaction product at a'temperature in the range of from about 200 F.
• inorganic basic compound being selected from the class consisting "of inorganic basic compounds of alkali metals and inorganic basic compounds of alkaline earth metals and said alcohol-containing solvent providing from about 2 to about 15 mols of aliphatic alcohol per mol of inorganic basic compound.
• tergent neutralized reaction product prepared by the process comprising reacting a normally liquid hydrocarbon with from about 1% to about 50% of a phosphorus sulfide at a temperature in the range of from about 200 F. to
• an alcoholcontaining reaction solvent wherein the alcohol is an aliphatic alcohol having from 1 to 7 carbon atoms, and reacting the resulting reaction mixture with from about 0.8 to about 5.0 mols of an inorganic basic compound of a metal selected from the class consisting of alkali metals and alkaline earth metals per mol of phosphorus in said reaction product at a temperature in the range of from about 120 F. to about 400 F. in the presence of said reaction solvent, said reaction solvent being present in the reaction mixture in an amount suflicient to provide from about 2 to about 15 mols of said aliphatic alcohol per mol of inorganic basic compound.
• composition of claim 4 wherein said normally liquid hydrocarbon is a butene polymer having a molecular weight of from about 150 to about 50,000.
• an oil-soluble detergent neutralized reaction product prepared by the process comprising reacting a normally liquid hydrocarbon with from about 1% to about 50% of a phosphorus sulfide at a temperature in the range of from about 200 F. to about 600 F., hydrolyzing the reaction product at a temperature in the range of from about 200 F.
• reaction solvent being present in the reaction mixture in an amount suflicient to provide from about 2 to about 15 mols of methanol per mol of barium oxide and filtering the resulting neutralized product to remove inorganic contaminants therefrom.
• a lubricant composition comprising a major proportion of a normally liquid lubricating oil and from about .002 to about 15% of the composition of claim 1.
• a lubricant composition comprising a major proportion of a normally liquid lubricating oil of from about .002 to about 15% of the composition of claim 4.
• An addition agent concentrate for lubricating oils consisting essentially of a lubricating oil containing more than about 15% of the oil-soluble neutralized reaction product of claim 1, said concentrate being capable of dilution with a normally liquid lubricating oil to a concentration of said reaction product in the range of from about .002 to about 15%.
• An addition agent concentrate for lubricating oils consisting essentially of a lubricating oil containing more than about 15 of the oil-soluble neutralized reaction product of claim 4, said concentrate being capable of dilu tion with a normally liquid lubricating oil to a concentration of said reaction product in the range of from about .002 to about 15 11.
• a process for making new and useful oil-soluble detergent neutralized phosphorus sulfide-hydrocarbon reaction products which process comprises reacting a hydrolyzed phosphorus sulfide-hydrocarbon reaction product, said hydrolyzed product having been prepared by reacting a normally liquid hydrocarbon with from about 1% to about 50% of a phosphorus sulfide at a temperature in the range of from about 200 to about 600 F.
• inorganic basic compound being selected from the class consisting of the inorganic basic compounds of alkali metals and the inorganic basic compounds of alkaline earth metals and said alcohol-containing solvent providing from about 2 to about 15 mols of aliphatic alcohol per mol of inorganic basic compound.
• a process for producing new and useful oil-soluble detergent neutralized phosphorus sulfide-hydrocarbon reaction products comprises reacting a hydrolyzed phosphorus sulfide-hydrocarbon reaction product, said hydrolyzed product having been prepared by reacting a normally liquid hydrocarbon with from about 1% to about 50% phosphorus sulfide at a temperature in the range of from about 200 to about 600 F.

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• 1960
  • 1960-01-07 US US956A patent/US3086941A/en not_active Expired - Lifetime
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  • 1960-12-30 FR FR848450A patent/FR1281515A/fr not_active Expired
• 1961
  • 1961-01-05 DE DEST17313A patent/DE1290647B/de active Pending
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