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
  • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
  • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
  • C10M137/04—Phosphate esters
• • 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
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
  • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/26—Organic compounds containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/26—Organic compounds containing phosphorus
  • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
  • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/108—Residual fractions, e.g. bright stocks
• • 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
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
  • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
• • 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
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
• • 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
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/22—Acids obtained from polymerised unsaturated 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
  • C10M2207/282—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
  • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2211/08—Halogenated waxes
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/26—Amines
• • 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
• • 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
  • C10M2223/041—Triaryl phosphates
• • 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
  • C10M2223/042—Metal salts thereof
• • 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
• • 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
  • C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • 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
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/10—Semi-solids; greasy
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B3/00—Engines characterised by air compression and subsequent fuel addition
  • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

• This invention deals with novel compositions of matter. This invention further deals with lubricant compositions. This invention also deals with fuel compositions. It further deals with lubricating compositions that exhibit effective dispersant detergent properties. It further deals with fuel compositions that exhibit eflfective anti-rust, anti-icing, carburetor detergency and sludge dispersing activity.
• compositions are produced by incorporating into a fuel or lubricant base at least one of the following pairs of compounds:
• R is an alkyl group of 8 to 18 carbon atoms and x is a number from 3 to 10; R is an alkyl group of 4 to 18 carbon atoms and y is a number from 2 to 12; and R represents alkyl groups having a total carbon atom content of 5 to 36, or hydrogen, at least two of the R embodiments being alkyl; R represents hydrogen or methyl and z is a number from 2 to 20.
• the symbols x, y and 2 represent numbers designating the amount of ethylene oxide in the compounds. It is to be understood by those skilled in the art that these numbers represent average values and frequently with compounds of this type there actually are mixtures of various amounts of ethylene oxide.
• This invention contemplates this known condition of ethylene oxide addition products. This invention contemplates the use of one or two moles of propylene oxide for the same amount of ethylene oxide in any of the above-described addition products. Propylene oxide and ethylene oxide are equivalent to that extent in the present invention.
• Typical embodiments of R include octyl, isodecyl, tertiary-dodecyl, tetradecyl and octadecyl.
• Typical embodiments of R include tertiary-butyl, hexyl, tertiary-octyl, nonyl, isodecyl, tertiary-dodecyl, tetradecyl and octadecyl.
• Typical embodiments of R include hydrogen, methyl,
• R represents hydrogen and methyl.
• R may be located at any available position but is usually and preferably in the para position with respect to the ethylene oxide chain.
• R, R and R alkyl groups may be normal, iso, tertiary or any other possible structural arrangement, just so the size of the group is observed.
• the secondary and tertiary phosphate ester compounds employed in the composition of the present invention are made by reacting phosphorous oxychloride with a selected alcohol, such as R(OCH2OH2):OH
• the phosphate esters employed in the compositions of this invention are produced by the process of this invention in varying amounts, but always with at least 50% of the tertiary phosphate ester present. It is preferred to have at least 60% of the tertiary phosphate ester present based on the phosphorus-containing products obtained. The remaining phosphorus-containing compound is the secondary ester, as indicated hereinbefore. As long as there is at least 50% or preferably 60% of the tertiary phosphate ester present in the phosphorus-containing product of the present process, the Valuable results of the present invention are consistently observed.
• reaction system that is as moisture-free as possible since any appreciable amount of moisture will react with the phosphorous oxychloride and thereby minimize the amounts of desired product obtained.
• a small amount of amine may be employed in the reaction product and there act as a scavenger for any residual hydrogen chloride present and thereby lower the acidity of the product.
• the polyoxyethyleneated straight and branched chain aliphatic and alkylphenyl alcohols which are to be converted to the secondary and' tertiary phosphate esters, as described hereinbefore, can readily be obtained by con: densing the selected alcohol with from 2 to 20 moles of ethylene oxide.
• Processes for effecting the ethoxylation are known in the art.
• the aliphatic alcohol of alkylphenyl alcohol is made slightly basic by the addition of a suitable alkali, such as an alkah metal or its hydroxide, carbonate or alcoholates, such as potassium hydroxide, sodium carbonate, potassium butoxide or the like.
• ethylene oxide is added and condensed.
• the reaction occurs at temperatures between 120" and 220 C.
• Suificient ethylene oxide is added to incorporate the desired amount according to the symbols x, y and 2, as mentioned hereinbefore.
• Small amounts of propylene oxide may be substituted, as stated pre- 'viously, and remain within the gamut of this invention.
• the secondary and tertiary phosphate esters of this R, R R and R particularly with respect to the amounts of ethylene oxide in the molecule concerned.
• compositions of the present invention are produced by incorporating from about 0.001% to 10.0% by weight ofat least one of the above-described secondary and tertiary phosphate esters in the oil or fuel base contemplated.
• the preferred range is about 0.005 to 2.0% by weight.
• the compounds of the present invention are used in the amounts of 0.1% to 10.0%, preferably 0.2% to 2.0% by weight.
• the range is 0.001% to 0.1%, preferably 0.005% to 0.05 by weight.
• the present compositions are also highly advantageous when employed in gasoline, which is stored over alkaline water in that there is no leaching out of the additive into the water layer. This is in contrast to amine salts of phosphorus-containing acids which characteristically split and dissolve in the water layer and thereby minimize and sometimes substantially eliminate any advantages that might otherwise be achieved.
• distillate fuels contemplated are those that boil from 75 to 750 F. which includes gasolines, along with jet and diesel fuels and furnace oils.
• the present compounds are particularly useful in fuels that boil up to about 600 F., that is, the normal gasolines and jet fuels.
• the need for an additive to supply all of the aforementioned qualities is widely recognized in the art, since the presence of rust, stalling, sludge deposition or pre-ignition properties and combinations thereof in oils and fuels leads to a marked diminution of the value of such lubricating oils or fuels.
• Lubricating compositions of this invention may be based on mineral oils or on synthetic lubricants.
• the mineral oils may vary over a wide range of viscosity, such as l to 25 centistokes at 210 F. These oils may be of naphthenic or paraflinic nature or may be of various mixtures. They may be distillates or mixtures of neutral oils and bright stocks.
• the lubricants may be bodied or gelled and used. as greases, if desired.
• the oils may vary from spindle oils or hydraulic oils to oils for reciprocating aircraft engines. They include oils for sparking combustion and compression ignition engines, varying from grades identified as.S.A.E. 5 to S.A.E. 50. Other types of lubricants are also included, such as hydraulic and automatic transmission fluids.
• the synthetic lubricants include esters, such as dioctyl or dinonyl adipates, azelates or sebacates. When use as hydraulic fluids is contemplated, phosphate esters are included as a base.
• the present compounds were subjected to astandard carburetor icing test, which is a test to evaluate the stall ng characteristics of a fuel.
• the test employed a 1957 Buick engine, equipped with a factory radiator, manifold, car-' buretor, and an automatic choke.
• the motor parts were stabilized at 40:L4 F.
• the test was conducted at 40i-4 F. and 90% humidity.
• the motor was ac-1 celerated to 1500 r.p.m. for one minute and then reduced to idle for 30 seconds. If the engine stalled, such was celerated to 15.00 r.p.m. and the cycle was repeated. This was continued until the engine was completely warmed up and the number of stalls was recorded.
• compositions of this invention were subjected to an anti-rust test, ASTM D-665, Procedure A, for dis tilled water, modified to use isooctane at 75 F. for a period of 24 hours.
• the compositions of the present invention were particularly elfective in this test, especially when the selected secondary and tertiary phosphate ester was employed in a total amount of 0.01% by weight.
• Many of the secondary and tertiary phosphate esters employed in the compositions of this invention substantially eliminated rust in this test even when used in amounts as low as 0.005% down to 0.001% by weight.
• Particularly outstanding in this respect are the following pairs of compounds:
• compositions of the present invention were evalu .ated in a standard carburetor detergency test.
• a standard carburetor detergency test In this evaluation there was employed a 1954 model, 6-cylinder Oak engine.
• the carburetor was equippedwith a clear plastic throttle body.
• the crankcase blowby from the engine was returned to the carburetor air inlet.
• the engine was operated on a base fuel under cyclic conditions for one hour to buildup a black deposit on the carburetor.
• the test was then continued for an additional five hours.
• Theevaluation . was based on the percent clean-up of the black deposit.
• compositions of the present invention led to clean-ups of about 20% to 25%.
• the compositions of the present invention were at least as efilcient and some exceeded 25% clean-up, when there was employed 0.02 gram of present phosphate esters per 100 ml. of fuel, which is a commercial concentration.
• Particularly outstanding in this respect was the composition of the present invention containing:
• compositions of the present invention were subjected to a sludge dispersancy test, as described by F. L. Nelson, D. P. Osterhout and W. R. Schwindeman, Ind. Eng. Chem. 48, 1892 (1956).
• the test considered of preparing a liter of fuel oil containing a candidate additive for sludge dispersancy.
• this same fuel oil composition there was incorporated four grams of synthetic sludge.
• the oil was then circulated for one hour through a single stage oil burner pump containing a 100 mesh strainer.
• the sludge deposit on the strainer was collected and weighed.
• Commercially acceptable sludge dispersants led to less than 100 mg. accumulation of sludge.
• the fuel oil without any additive led to an accumulation of 250 mg.
• compositions of the present invention When one of the pairs of secondary and tertiary phosphate esters described hereinbefore was incorporated into the fuel oil to produce a composition of the present invention, there was obtained sludge accumulations of less than 100 mg. in most instances. When compositions of the present invention were employed in this test, the sludge accumulation was appreciably less than 100 mg. and in most cases gave 50 mg. accumulation and on several occasions ten or less. Concentrations of additives in the fuel oil generally ranged between 0.005 and 0.01 gram per 100 ml. of fuel oil. Particularly outstanding in this evaluation were:
• compositions of the present invention were evaluated as detergents and dispersants for lubricating oils according to the Panel Coker test.
• the Panel Coker Test is described in the record of the Fifth World Petroleum Congress (1959) in an article by R. M. Jolie, Laboratory Screening Test for Lubricating Oil Detergents and Dispersants.
• a sample of a compound under test was dissolved in an oil containing 1.0% of a thermally unstable Zinc dialkyldithiophosphate. The solution was placed in a heated pump and was splashed against a heated panel at 570 F. for two hours. Gain in weight of the panel was determined and compared against the weight of a panel which had been splashed with oil without the test compound.
• compositions of the present invention may be more fully understood from the following illustrative examples. Parts by weight are used throughout.
• Example 1 To 604 parts (1.38 moles) of an adduct of 5 moles of ethylene oxide and nonylphenol having a hydroxyl number of 128 is added with stirring at 5 to 15 C. during /1 hour, 61.5 parts (0.40 mole) of phosphorous oxychloride. The mixture is stirred /2 hour at 5 to 10 C. and then warmed to 25 C. during another /2 hour. The system is then evacuated to 20 mm. mercury and heated to C. during one hour. Stirring is continued for 4 /2 hours at 100 to 110 C. at 10 to 20 mm. Hg while hydrogen chloride is removed. The mixture is cooled and analyzed. It contains 2.12% phosphorus, 0.71% total chlorine, no ionizable chlorine, has an acid number of 3.7 and a hydrolyzable acid number of 13.4.
• the mixture is then cooled to 10 C., care being taken to exclude moisture, and there is added 15.3 parts (0.10 mole) of phosphorous oxychloride during A1 hour at 5 to 10 C.
• the mixture is then war-med to 45 C. in 1% hours.
• a vacuum line is attached to the system and the pressure is reduced to 50 mm. Hg.
• the temperature is then raised to 100 C. during another hour and the mixture is then stirred at 100 to 110 C. at 5 to 10 mm. Hg for two hours.
• a sample, A is removed, which weighs 47.5 parts.
• the remainder, 92.5 parts is diluted with 2.3 parts of a C C tertiary alkyl primary amine 7 to'bring the pH to 7 to 8 as measured by Bogens Universal Indicator.
• the product, B is submitted along with A for evaluation as a gasoline or lubricant additive. Both products are excellent as fuel and lubricant additives.
• the secondary and tertiary phosphate ester products
• Example 3 Example 2 is repeated except that 257 parts (0.345 mole) of an ethylene oxide adduct of dinonylphenol containing 9 moles of ethylene oxide per mole of dinonylphenol. A sample of 79 parts of product is removed and the remainder, 182 parts, is diluted with 4 parts of a C -C tertiary alkyl primary amine to raise the pH to 7 to 8. Both are valuable additives for fuels and lubricants.
• the secondary and tertiary phosphate ester products have the formulas:
• Example 4 To a stirred mixture of 92.5 parts (0.246 mole) of the addition product 'of 4 moles of ethylene oxide to tridecyl alcohol and 24 parts (0.24 mole) of triethylamine is added dropwise during 4 hour, 11.5 parts (0.075 mole) of phosphorous oxychloride while the temperature is held below 55 C. by external cooling. The mixture is stirred another three hours at 50 to 55 C., filtered, allowed to stand overnight and refiltered.
• the phosphorus ester product is a mixture of:
• a mixture of 100 parts of toluene, 118.6 parts (0.30 mole) of the addition product of 4 moles of ethylene oxide to nonylphenol and 30.6 parts (0.30 mole) of triethylamine is added dropwise over a period of two hours to a stirred mixture of 15.3 parts (0.10 mole) of phosphorous oxychloride and 100 parts of toluene at 0 to 5 C.
• the mixture is stirred another two hours at 0 to 5 C., warmed to room temperature, filtered tree of the precipitated triethylamine hydrochloride and poured slowly into excess dilute sodium hydroxide solution with stirring and cooling.
• the upper layer is separated and the lower aqueous layer is washed with toluene.
• the toluene extract is combined with the upper layer, which is then stripped free of solvent, taken up in heptane and allowed to stand overnight.
• the supernatant liquid is decanted from a small salt residue, filtered and stripped free of solvent to yield 78 parts of clear amber colored oil.
• the phosphorus ester product is a mixture of:
• the phosphorous ester products have the formulas:
• Example 9 To a stirred mixture of 129.4 parts of (0.22 mole) of an adduct of 7.45 moles of ethylene oxide to a mixture.
• the final step in the reaction is the hydrolysis of the reaction mixture according to the procedure of Example 1, using 10% by weight of water based on the reaction mixture.
• the product identification then follows this hydrolysis in all cases;
• a composition comprising a major amount of a substance selected from the class consisting of normally liquid hydrocarbon fuels and lubricants containing a minor 9 amount sufficient to inhibit rust of a member selected from the group of pairs consisting of:
• R is alkyl of 4 to 18 carbon atoms
• R is a member of the class consisting of hydrogen and 25 alkyl in which the R embodiments total 5 to 36 carbon atoms, at least two of the R embodiments representing alkyl, R is selected from the class consisting of hydrogen and methyl
• 3 y is a number of 2 to 12
• z is a number of 2 to 20, the t-phosphate ester being present in the amount of at least 50% of each of said pairs.
• composition according to claim 1 in which said member is a mixture of:
• a normally liquid hydrocarbon fuel containing from 0.001% to 0.1% by weight of a mixture of:
• a normally liquid hydrocarbon fuel containing from 0.001% to 0.1% by weight of a mixture of:
• a normally liquid hydrocarbon fuel containing from 0.001% to 0.1% by Weight of a mixture of:
• a lubricant containing from 0.1% to 10.0% by weight of a mixture of:

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Lubricants (AREA)
• Liquid Carbonaceous Fuels (AREA)

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Citations (10)

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• 0
  • DE DENDAT1251584D patent/DE1251584B/de active Pending
  • NL NL302079D patent/NL302079A/xx unknown
• 1963
  • 1963-12-05 US US326658A patent/US3340191A/en not_active Expired - Lifetime
  • 1963-12-14 ES ES294501A patent/ES294501A1/es not_active Expired
  • 1963-12-17 DE DER36811A patent/DE1265330B/de active Pending
  • 1963-12-18 BE BE641455A patent/BE641455A/xx unknown
• 1965
  • 1965-12-03 GB GB49779/63A patent/GB1069079A/en not_active Expired

Patent Citations (10)

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