US3919094A - Additives for lubricants and motor fuels - Google Patents

Additives for lubricants and motor fuels Download PDF

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US3919094A
US3919094A US50394674A US3919094A US 3919094 A US3919094 A US 3919094A US 50394674 A US50394674 A US 50394674A US 3919094 A US3919094 A US 3919094A
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reaction
sulfonic acid
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petroleum
viscosity
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Sidney Schiff
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Phillips Petroleum Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/24Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2493Organic compounds containing sulfur, selenium and/or tellurium compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/08Aldehydes; Ketones
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/14Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26Amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions

Abstract

Improved additives for lubricants and motor fuels are provided by a process comprising reacting a petroleum sulfonic acid with an adduct formed from an amine and an aldehyde. Lubricating oil compositions and motor fuels containing said additives are also provided.

Description

United States Patent $611111 1451 Nov. 11, 1975 [54] ADDITIVES FOR LUBRICANTS AND 2.906.613 9/1959 M1115 44/11 OTO FUELS 3.043.783 7/1962 Hatchcr ct nl. 44/73 3.264.894 l2/l94l Shoemaker el al. 44/73 [7 Inventor: Sidney Schiff. Bartlesviue. Okla. 34111.1 17 9/l968 SChiff 252/33 3.438.898 4/l969 Schloholm ct al. 151/33 [73 1 Asslgnee' gl' fif gir Compan) 3.441.369 4/1969 McCoy e1 .11. 260/965 R 3.615.294 10/1971 Von Allrnen N 44171 [22] Filed: Sept. 6, 1974 Primary E.\'u1r11'I1erDaniel E. Wyman [2H Appl' 303346 Ass/slum Emnu'ner-Mrs Y. H. Smith [52] US. Cl. 252/33; 44/73; 44/76 [5|] Int. Cl ClOm 1/40 [57} I ABSTRACT 5 Field f Search H 252/33; 44/73 76; Improved addltwes for lubncants and motor fuels are 260/5012 provided by a process comprising reacting a pctro leum sulfonic acid with an adduct formed from 1111 [5 References Cited amine and an aldehyde. Lubricating oil compositions UNITED STATES PATENTS and motor fuels containing said additives are also pro- "d d. 172L843 10/1955 Palmer. 11 253/33 H e 2.831.8[0 4/!958 Wilson 252/33 l0 Claims. N0 Drawings ADDITIVES FOR LUBRICANTS AND MOTOR FUELS This invention relates to improved additives for lubricants and motor fuels. in one aspect, this invention relates to the preparation of novel compositions of matter formed from petroleum sulfonic acids and an adduct formed from an amine and an aldehyde. In accordance with another aspect, this invention relates to lubricant compositions containing as an additive the reaction product formed from a petroleum sulfonic acid and an adduct from an amine and an aldehyde. ln accordance with another aspect, this invention relates to motor fuel compositions containing as an additive the reaction product formed by contacting a petroleum sulfonic acid with an adduct of an amine and an aldehye.

At the present time it is common practice to enhance or modify certain of the properties of lubricating oils through the use of various additives or improvement agents. The lubricating oils employed in internal combustion engines, such as automotive, light aircraft, and diesel engines, in particular, require the use of additive agents to render them serviceable under the adverse environmental conditions frequently encountered in the operation of these engines. Among the various additives employed in modern engine oils, one of the most important is the type which acts to prevent accumulation of sludge in the crankcase and on the cylinder walls, thereby preventing sticking of the piston rings, and the formation of varnish-like coating on the pistons and cylinder walls. Because of their general function of maintaining a clean engine, additives of this nature are termed detergents although it is now understood that they have little utility in cleaning a dirty engine but by virtue of dispersant activity prevent or greatly retard engine fouling.

As cleanliness requirements have called for greater concentrations of detergent additives, the problem of ash deposition in the combustion chamber has become more serious. Especially is this a problem in certain engines which tend to develop violent preignition troubles in the presence of metal-containing ash. These problems have increased the importance and desirability of using ashless" detergents.

An ashless detergent is one which shows substantially no ash when tested by ASTM procedure D-482- 59T. The only possible source of metal when using such an additive is that of corrosion products and trace quantities present in some crude oils. It can be generally stated that metal-containing deposits in an engine (I) contribute to valve burning, (2) contribute to preignition, (3) tend to foul and short-out spark plugs, and (4) tend to increase octane requirements. Use of conventional metal-containing detergents can contribute to the deposit of metal-containing materials in the combustion chamber. Metal-containing deposits do not form from ashless detergents. Use of an ashless detergent, therefore, materially reduces the problems normally encountered in internal combustion engines in connection with metal-containing deposits.

It has been found that reaction products having improved detergent and dispersant properties can be prepared by reacting a petroleum sulfonic acid with an aduct formed from at least one amine and at least one aldehyde. Thus, broadly speaking, the present invention resides in the reaction product or products obtained when a petroleum sulfonic acid is reacted with an adduct formed from at least one amine and at least 2 one aldehyde as new additives for lubricants and motor fuels; methods of preparing said new additives; and lubricant and motor fuel compositions containing said new additives.

An object of this invention is to provide an ashless additive for lubricants.

Another object of this invention is to provide improved additives exhibiting reduced deposit-forming tendencies in motor fuels.

Another object of this invention is to provide a method for the preparation of additives for lubricating oils and motor fuels.

Another object of this invention is to provide an improved lubricating composition utilizing the additives of the invention.

Another object of this invention is to provide improved motor fuel compositions utilizing the additives of the invention.

Other aspects, objects, and advantages of the invention will be apparent to those skilled in the art upon studying this disclosure.

Thus, according to the invention, there is provided new compositions of matter comprising the oil-soluble reaction product or products obtained upon reacting a petroleum sulfonic acid with an adduct formed from at least one amine and at least one aldehyde.

Further according to the invention, there is provided a process for producing an additive for lubricants and motor fuels which process comprises forming an adduct from at least one amine and at least one aldehyde, and then reacting the adduct thus formed with a petroleum sulfonic acid to form said additive.

Further according to the invention, there is provided as a new additive for lubricants and motor fuels a product additive obtained by the process described in the preceding paragraph.

Still further, according to the invention, there is provided new lubricating oil compositions comprising a major proportion of a lubricating oil base stock and a minor proportion of a new additive in accordance with the invention.

Still further, according to the invention, there is provided a new motor fuel composition comprising a major proportion of a motor fuel and a minor proportionof a new additive in accordance with the invention.

A wide variety of reaction conditions can be employed in the practice of the invention. Any reaction conditions under which the reactions involved in the invention will take place are within the scope of the invention. Similarly, any proportions of reactants which will react with each other to produce a product additive of the invention are within the scope of the invention. However, as will be understood by those skilled in the art in view of this disclosure, certain reaction conditions and reactant proportions are favored for economic reasons, i.e., the reactions proceed faster and give greater yields for some reaction conditions and some proportions of reactants. The reaction or reactions involved in preparing the product additives of the invention can be carried out in the presence or absence of a diluent which is chemically inert, i.e., does not react with the reactants or reaction products.

Generally speaking, in the practice of the invention the petroleum sulfonic acid and amine/aldehyde adduct are preferably reacted in amounts ranging from 1/1 to 5/1 equivalents of petroleum sulfonic acid/mole of amine used to prepare the adduct. A preferred range is l.5/l to 3.5/1. Generally speaking, sufficient petro- 3 leum sulfonic acid is used with the amine adduct to obtain a hydrocarbon-soluble reaction product. However, it is within the scope of the invention to employ operable ratios of sulfonic acid to adduct outside said ranges.

The reaction of said adduct and said petroleum sulfonic acid can be carried out at any temperature at which the reaction(s) involved will proceed. Generally speaking, said reaction is preferably carried out at temperatures within the range of from about 100 to about 200F. However, it is presently preferred to employ temperatures in the range of 140 to 150F although it is within the scope of the invention to employ operable temperatures outside said ranges.

A wide range of reaction times can be employed in the practice of the invention. Generally speaking, the reaction times employed for the reaction of said reactants will be within the range of from about 0.] to about 20 hours. However, it is within the scope of the invention to employ operable times outside said ranges. The reaction can be conducted at any pressure, such as atmospheric pressure, suitable for carrying out the reactions involved.

lt is currently preferred to contact the reactants in the presence of an inert diluent, the most preferred of which is a SAE largely paraffinic lubricating oil base stock in amounts ranging from 0.2/1 to 10/1 parts by weight diluent per part by weight petroleum sulfonic acid. It is likewise currently preferred to add a solution of petroleum sulfonic acid in SAE 10 stock oil (approximately 60 weight percent petroleum sulfonic acid) slowly to a rapidly stirred dispersion of amine/aldehyde adduct in SAE 10 stock oil (approximately 30 weight percent adduct) while maintaining the temperature of the reaction system at 140 to 150F.

If the currently preferred reaction conditions are employed, no further isolation or purification steps are necessary in order to use the product in gasoline or lubricating oil formulations. lt is currently preferred to employ the crude reaction mixture for such purposes as described above without subsequent treatment. In some cases, however, it may be desirable to isolate and purify the product. Such may be accomplished by any methods currently known in the art, such as fractional crystallization, solvent extraction, etc.

Generally speaking, any petroleum sulfonic acid prepared in accordance with methods known in the art can be used as a starting reagent in the practice of the invention. Methods disclosed in US. Pat. No. 3,135,693, issued June 2, 1964, to W. B. Whitney et al. are exemplary of methods which can be used in preparing sulfonic acids which can be used in the practice of this invention.

A wide variety of oils can be used as the charge oil in preparing the petroleum sulfonic acids used in the practice of the invention. Preferably, said charge oil is selected from more viscous bright stock fractions of petroleum. A petroleum fraction having a viscosity of at least 90 SUS at 210F will produce a petroleum sulfonic acid which is satisfactory in many instances. The deasphalted and solvent refine petroleum fractions having a viscosity of about 140 to about 270 SUS at 2l0F are preferred. A presently more preferred sulfonation charge stock is a propane fractionated, solvent extracted, and dewaxed Mid-Continent oil of about 200 to about 230 SUS at 210F. It is preferred that the sulfonation charge stock have a viscosity index of about 85 to I00, or even higher.

A Mal-Continent oil is more precisely defined as a mixed base or intermediate base oil in The Science of Petroleum," Volume 1, page 7, Oxford University Press, London, New York and Toronto, 1938. The base ofa crude petroleum is defined therein as follows: The 'baseof a crude petroleum is descriptive of the chemical nature of its main constituents. A petroleum may be described as paraffin base, asphalt base, or mixed base (intermediate base), according as paraffin wax, asphalt, or both paraffin wax and asphalt are present in the residue after distillation of the lighter components. Typical representatives of these three classes are Pennsylvania, Mexican, and Mid-Continent petroleums, respectively."

The residual material discarded from the propane fractionation step contains the rejected asphalt and more aromatic oils. The lube oil fraction, recovered in a propane fractionation step after removal of the SAE 50 lube stock, is extracted with a selective solvent which will separate the paraffinic hydrocarbons from the more aromatic-type hydrocarbons for removal of these more aromatic-type hydrocarbons to prepare the preferred feed-stock. The raffinate from the solvent extraction step is then dewaxed.

Sulfonating agents which are known to the art can be utilized in the sulfonation step in preparing said petroleum sulfonic acids. sulfonating agents which can be so used include fuming sulfuric acid and liquid S0,. Said fuming sulfuric acid can vary from l0 weight percent to 40 weight percent excess However, when sulfuric acid is used it is usually preferred to use commercial fuming sulfuric acid which contains about 20 weight percent excess 80;. Liquid S0 i.e., liquid SO; in liquid S0,, is the presently preferred sulfonating agent for use in the practice of the invention. Such liquid 80, is commercially available.

When 20 percent fuming sulfuric acid is used as the sulfonating agent, the acid-oil ratio can be in the range of from about 01:1 to about 0.7:], or even [:1 to produce the petroleum sulfonic acids used in the practice of the invention. A preferred range of acid-oil ratios is in the range of about 0.3 to about 0.6:l. When liquid SO, in liquid S0, is the sulfonation agent, the S0, to oil weight ratios are maintained equivalent to those available from the 20 percent fuming sulfuric acid values given above. In other words, the 80;, to oil ratio can be in the range of about 0.02 to 0.2, preferably about 0.06 to about 0.12:1. Said S0, to oil ratios can be controlled by varying the rate of flow of the oil or of the SO,containing medium, or both. The above given ratios are weight ratios.

Sulfonation temperatures can be controlled within the range of about 50 to about 200F with the preferred operating range being between about 80 and about 150F. At temperatures above about 200F, excessive oxidation with liberation of sulfur dioxide may take place. A reaction time of about 20 to about minutes is preferred when fuming sulfuric acid is utilized as the sulfonating agent in order to provide optimum yield and quality of products. When sulfur trioxide, e.g., sulfur trioxide in sulfur dioxide, is utilized as the sulfonation agent, the reaction rate is greatly accel erated and the reaction has been found to be substantially completed in the time required to accomplish suitable contact of the oil with the sulfur trioxide, usually less than about 5 minutes.

The sulfonation reaction can be carried out at atmospheric pressure although pressures greater or less than atmospheric also can be employed, if desired. When using liquid 80;, in liquid SO, as the sulfonating agent, it is preferred to carry out the reaction at sufficient pressure to maintain the 80 in liquid phase.

As indicated hereinbefore, the above-described petroleum sulfonic acids are reacted with an adduct formed from at least one amine and at least one aldehyde to produce the product additives of the invention.

A wide variety of amines can be used in the practice of the invention. Presently preferred amines for use in the practice of the invention include (a) those containing from 2 to 12 carbon atoms per molecule and represented by the formula RNHg wherein R is alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkylaryl, or arylcycloalkyl and (b) those polyamines represented by the formula H N[(CH,),NH],,H wherein at is a whole integer of from 2 to 6, inclusive, and y is a whole integer of from 1 to l0, inclusive. Examples of suitable amines which can be used in the practice of the invention include, among others, the following: ethylamine, butylamine, S-methylcyclopentylamine, decylamine, dodecylamine, cyclohexylamine, aniline, naphthylamine, 3,5-diethylcyclohexylamine, m-toluidine, 2,3-xylidine, benzylamine, 3-cyclohexylbutylamine, p-cyclohexylaniline, 4-phenylcyclohexylamine, 3-methyl-4-phenylcyclopentylamine, ethylenediamine, and its homologs, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, butylenediamine, hexamethylenediamine, tetrahexenepentamine, heptabutyleneoctamine, decapenteneundecamine, and the like.

Aldehydes generally corresponding to the formula 0 his and containing from 2 to 12 carbon atoms per molecule are useful in this invention. Each R is a radical selected from hydrocarbyl, hydroxyhydrocarbyl, hydrocarbyloxyhydrocarbyl, halohydrocarbyl, hydrocarbylthiohydrocarbly, and mercaptohydrocarbyl wherein the term hydrocarbyl describes the radicals alkyl, cycloalkyl, aryl, or combinations of these such as aralkyl, or alkaryl, and the like. R is preferably a hydrocarbyl, hydroxyhydrocarbyl, or a hydrocarbyloxyhydrocarbyl radical. Examples of aldehydes which are within the scope of this invention includes acetaldehyde, butyraldehyde, valeraldehyde, dodecylaldehyde, benzaldehyde, p-tolualdehyde, a-tolualdehyde, cyclohexylaldehyde, p-anisaldehyde, 4cyclopentylbutyraldehyde, salicylaldehyde, p-chlorobenzaldehyde, o-mercaptobenzaldehyde, 2,2,3,-trichlorobutanal, p-(methylthio)benzaldehyde, and the like. Valeraldehyde, salicylaldehyde, and p-anisaldehyde are especially preferred aldehydes.

The adducts of the above-described aldehydes with amines are prepared by contacting the reactants in amounts ranging from about 1/1 to about 2/1 moles of aldehyde per mole of amine. A preferred range is from 1/1 to about 1.25/1. Said contacting is done under any suitable conditions of time, temperature, and pressure which result in the desired product. It is currently preferred to add the aldehyde to the amine slowly with stirring while cooling the reaction mixture to temperatures as low as about 0F. The reaction mixture can then be refluxed at temperatures up to about 350F to complete the reaction and to distill some of the water formed in the reaction. The total reaction time can range from about 0.l to about 20 hours. The product can then be purified by conventional means, such as solvent extraction, fractional distillation, azeotropic distillation, addition of a drying agent such as potassium hydroxide, etc., but it is preferable to use the crude reaction mixture without further purification.

[t is sometimes desirable to pressurize the reactor with an inert gas to maintain the adduct forming reactants predominantly in the liquid phase, for example, from 0 to about 2000 psig.

On occasion, it is desirable to employ an inert diluent in the production of the adduct of the amine and aldehyde. Such diluents include saturated aliphatic and cycloaliphatic hydrocarbons, aromatic hydrocarbons, etc. The presently preferred mode of operation is in the absence of diluent.

While it will be immediately evident to one skilled in the art that the reaction of aldehydes with amines produces predominantly imines, the scope of this invention encompasses the products, mixtures of products or crude reaction mixtures obtained by contacting under appropriate conditions the above-described aldehydes and amines.

The adduct of the amine and aldehyde can be isolated and purified by any convenient means, such as fractional distillation, crystallization, solvent extraction, etc. However, it is currently preferred to employ the crude reaction mixture for contacting with the petroleum sulfonic acid to produce the inventive composition.

The compositions of this invention, when used as a gasoline additive, are added directly to gasoline in either a purified state or as a crude reaction mixture as hereinbefore described. The quantity of additive utilized is in the range of 0.00l to 0.2, preferably 0.0] to 0.1, parts by weight additive per 100 parts by weight gasoline. When gasoline containing this additive is utilized in conventional internal combustion engines, the buildup of hard refractory deposits on intake valves is substantially diminished. in addition, the additive in gasoline is effective as an upper cylinder lubricant, a carburetor cleaner, a solvent for valve deposits, and a fuel line cleaner.

The gasolines into which the invention additives are dispersed are conventional motor fuel distillates boiling in the range of 420F. Gasolines or automotive fuels to which the described additives perform the functions described include substantially all grades of gasoline presently being employed in automotive and internal combustion aircraft engines. Generally, automotive and aircraft gasolines contain both straight-run and cracked stock with or without alkylated hydrocarbons, reformed hydrocarbons, and the like. Such gasolines can be prepared from saturated hydrocarbons, e.g., straight-run stocks, alkylation products, and the like, with or without gum inhibitors and with or without soluble lead compounds as, for example, tetraethyl lead (T.E.L.) or ethyl fluid. The gasolines may contain as much as about 5 ml of T.E.L. per gallon, such amounts being used commercially in aviation gasolines. These can be leaded or non-leaded and can contain other conventional fuel additives such as antioxidants and the like.

The compositions of this invention are oil-soluble and can be incorporated in lubricating oil formulations in combinations depending on specific service requirements. For example, in many general duty crank-case oil applications, the additives of the invention can be blended with appropriate base oils and other additives to provide high quality lubricating oils which meet the requirements and specifications for their intended use.

Generally speaking, the compositions of this invention can be added to the base lubricating oil in any amount sufficient to produce the desired degree of improvement. For example, the additives can be used in amounts ranging from 0.2 to 30 weight percent of the finished oil. A presently preferred concentration of petroleum sulfonic acid addition product is in the range of about 1 to 15 weight percent of finished oil.

The lubricating oils to which the invention compositions can be added include any suitable mineral oils of lubricating viscosity, such as those used for compounding lubricating oils of SAE to SAE 50 viscosity. These oils can be derived from suitable naphthenic, paraffinic, and mixed base crudes. The lube oils can also contain other additives such as thickeners and the like.

EXAMPLE l in Run 1 a petroleum sulfonic acid was prepared from a solvent-refined, dewaxed lubricating oil fraction derived from Mid-Continent petroleum and having the following properties: viscosity of about 4200 SUS at 100F and about 210 SUS at 210F and viscosity index of about 97. This oil was sulfonated with a 10 percent SO -9O percent SO, mixture in a continuous operation substantially like that described by Whitney et al., US. Pat. No. 3,135,693. The SO /oil weight ratio was about 0.08, and the temperature of the reaction was controlled at about 1 F. The total reaction time, including mixing and soaking periods, was about five minutes. The system was maintained in liquid phase at a pressure of 100 to 120 psig. Effluent from the sulfonation unit was subjected to a two-stage flash for $0 -$0 removal.

EXAMPLES ll to VII The following runs illustrate the preparation of adducts of tetraethylenepentamine (TEPA) and either salicylaldehyde, valeraldehyde or p-anisaldehyde.

The general method of preparation of the adducts is illustrated by Run 2 in which the reaction product of TEPA and salicylaldehyde was prepared.

Run 2 was conducted in a 250 ml reactor equipped with a condenser, stirrer and addition funnel and cooled by partial immersion in an ice-water bath. To 47.5 gm of stirred TEPA in the reactor, 30.5 gm salicylaldehyde was added through the addition funnel over a 45-minute interval. Following completion of the aldehyde addition, the stirring at ice-water temperature was continued for 15 additional minutes, after which the reaction mixture was refluxed for 1.5 hours. Elemental analyses of the crude reaction product are tabulated in Table 1.

Run 3 was conducted as described for Run 2 except that double amounts of reactants and a 500 ml reactor were used. Addition of salicylaldehyde required 1.25 hours. Following refluxing at about 268F, the reaction mixture was cooled to F, 200 ml of benzene was added, and mixture was heated to azeotropically distill a benzene-water mixture. Following distillation of benzene the reaction mixture was heated to 290F with a stream of nitrogen bubbling through the mixture to remove residual water. Crude reaction mixture (145.8 gm) was retained as product. Elemental analyses are recorded in Table l.

Run 4 was conducted in the reactor described for Run 2 using 95 gm TEPA and 43 gm valeraldehyde. Addition of the valeraldehyde to the stirred TEPA cooled in an ice-water bath required 1.75 hour, after which stirring continued at that temperature for an additonal 15 minutes. A 70 ml aliquot of the reaction mixture was refluxed for 1.5 hours. Elemental analyses of the crude product are recorded in Table I.

In Run 5 the remainder of the reaction mixture from Run 4 following removal of the 70 ml aliquot was used. To said remaining reaction mixture was added a small amount of potassium hydroxide. After one minute stirring, the mixture was allowed to stand overnight at about 0C. Decantation of the upper liquid layer and fractional distillation thereof gave product (b.p. 176-250C at 25 torr), the elemental analyses of which are recorded in Table Run 6 was conducted in the reactor described for Run 2 using 47.5 gm TEPA and 34 gm p-anisaldehyde. Dropwise addition of aldehyde to the stirred TEPA cooled in an ice-water bath required 1 hour, after which stirring continued at that temperature for 15 additional minutes. Refluxing the reaction mixture for 1.5 hours gave crude reaction mixture, the elemental analyses of which are tabulated in Table 1.

Run 7 was conducted as described for Run 6 except that the reflux step was omitted and the reaction mixture was then stirred with a small amount of potassium hydroxide for one minute and allowed to stand over potassium hydroxide overnight at 0C. Decantation of the resulting upper liquid layer and fractional distillation thereof gave product boiling at 167 to C at 13 torr. Elemental analyses of the product are tabulated in Table 1.

9 10 TABLE l-continued Run Starting Treat- Elemental Analyses No. Aldehyde meat %C bl-l %N 110 Theory 62.50 9.51 22.77 5.20

Not determined.

Calculated for imine C,.H N O. Calculated for starting mixture. Calculated for imine C ,H ,N.. Calculated for iminc C lt-D50. "Elemental analyses of individual fractions EXAMPLE VII] The following run illustrates the reaction of the petroleum sulfonic acid of Run 1 with the amine/- salicylaldehyde adduct of Run 3. The usefulness of the product as an additive for motor fuels and lubricating oils is also demonstrated.

In Run 8 in a 3-liter reactor were mixed 65 gm of salicylaldehyde/TEPA adduct from Run 3 and 390 gm SAE 10 stock oil. To the stirred suspension heated to 145F was added I430 ml of a solution consisting of 58.86 weight percent petroleum sulfonic acid in SAE l stock oil, said solution having previously been blown with nitrogen. Addition of the petroleum sulfonic acid solution required 70 minutes during which the temperature of the reaction system was maintained at l45F and after which stirring and temperature of l45F were maintained for an additional 30 minutes. The crude reaction mixture contained 0.8 percent sulfur and 0.6 percent nitrogen and exhibited a pH of 6.35.

This product was rated excellent when submitted to a carbon spot dispersancy test. A carbon spot dispersancy test is conducted by stirring 50 mg of carbon black into gm of an oil blend containing 4 weight percent of the candidate additive. A drop of the resulting slurry is then dropped onto a polished Burns Block heated to a temperature of 500F. The extent to which the carbon black is carried to the extremity of the resulting oil ring is a measure of the dispersancy characteristics of the additive.

The product of this run was also compounded into a commercial oil formulation and subjected to a standard automotive Ford Sequence VB test (described in ASTM Special Technical Publication No. 3l5-C) and compared to the SAE requirements (I973 SAE Handbook, Sec. J-l83a, SAE Recommended Practice for Engine Oil Performance," pp. 417-4 [9) for a lubricating oil. The results are tabulated in Table II.

A commercial SAE l0W-40 motor oil formulation containing calcium petroleum sulfonate, and index r This test formulation contained l2 weight percent of the additive of Run 8 in place of the normally used commercial dispersant.

Maximum values.

These data show that the invention additive equalled or surpassed the SAE requirement in three of the five test categories. Overall sludge and overall varnish were below standard.

A carburetor detergency test was carried out to test the crude reaction mixture of Run 8 as a motor fuel ad- TABLE lll Fuel Deposits (mg) Neat Fuel l7 Fuel with additive [3.6

Fuel contained 10 F'I'B (pounds per thousand barrels) of the crude reaction mixture of Run 8 These results show reduced deposit formation using this invention composition as a gasoline additive.

EXAMPLE [X The following run illustrates the reaction of the petroleum sulfonic acid of Run 1 with the amine/- valeraldehyde adduct of Run 4. The usefulness of the product as an additive for motor fuels and lubricating oils is also demonstrated.

In Run 9 in a 500 ml reactor were mixed 7.8 gm of crude reaction mixture from Run 4 and 10 gm SAE l0 stock oil. To the stirred suspension heated to I45F was added in increments a solution consisting of 58.86 weight percent petroleum sulfonic acid in SAE 10 stock oil, said solution having previously been blown with nitrogen. After each increment of acid oil was added and the reaction mixture stirred for 15 minutes, a l0 ml aliquot was removed from the reaction system for carbon spot dispersancy test (as described in Example VIII) and pH measurement. The results are tabulated in Table IV.

Equivalents of petroleum sull'onic acid added per mole of original TEPA. Not determined.

The aliquot, removed after a total of ml of petroleum sulfonic acid solution was added, was tested as a gasoline additive in a laboratory gasoline deposit test. The raw gasoline stock for this test was a commercial automotive premium gasoline containing tetraethyl lead and oxidation inhibitor but no other additives. The raw gasoline stock was passed through a 0.3 micron filter after which 0.04 parts by weight sulfurized terpene per I parts by weight filtrate was added. This procedure produced the gasoline source from which samples were taken for testing with and without the additives of this invention.

The test procedure utilized was a modification of the method described in A Bench Technique for Evaluating the Induction System Deposit Tendencies of Motor Gasolines, A. A. Johnston and E. Dimitroff (Society of Automotive Engineers, Fuels and Lubricants Meeting, Houston, Texas, Nov. l-3, 1966, Paper No. 660783). Briefly, in accordance with above modified procedure, the test gasoline (2 ml/min) was mixed with a flow of air (28 ft lhr) to form a gasoline-air mixture. The mixture was discharged from a nozzle as a spray against an aluminum deposit pan of known weight. The deposit pan which was preheated to 375F was maintained at that temperature while the mixture was sprayed against it. After 250 ml of test gasoline was sprayed, the gasoline flow was terminated, but the airflow and temperature were maintained constant for another minutes. The airflow was then terminated and the pan was allowed to cool to room temperature. Weighing of the pan then provided the weight of deposits in milligrams per 100 ml of test gasoline.

Results obtained using the above-described test on the base gasoline stock without and with 0.05 weight percent crude reaction mixture (that aliquot removed after l50 ml total petroleum sulfonic acid solution was added in Run 9 are given in Table V.

TABLE V Fuel Deposits (mg) Without additive l.5 With additive 0 The above data show the reduced deposit formation using this invention composition as a fuel additive and the excellent dispersant properties obtained using this invention composition as a lubricating oil additive.

EXAM PLE X TABLE VI Total Petroleum Sulfonic Acid Acid/Amine Carbon Spot Added. ml Ratio Test pH 50 0.603 Fair 8.9

150 2.32 Excellent+ 5.0

200 3.30 ND L8 TABLE ll-continued Total Petroleum Sulfonic Acid Acid/Amine Carbon Spot Added. ml Ratio Test pH 250 4.33 Excellent l.7

"Equivalent: of petroleum sulfonic acid added per mole of original TEPA. Not determined.

TABLE Vll Fuel Deposits g) Without additive With additive The above data show the excellent dispersant properties obtained using this invention composition as a lubricating oil additive and the reduced deposit formation using it as a fuel additive.

I claim:

1. A lubricating oil composition comprising a major proportion of a lubricating oil containing a small but effective amount, sufficient to impart decreased detergency to said lubricating oil, of an oil-soluble dispersant additive which is the reaction product obtained upon reacting a. a petroleum sulfonic acid with b. an adduct formed for l. at least one amine selected from primary monoamines having from 2 to 10, inclusive, carbon atoms, and polyamines represented by the formula H,N[(CH,),NH],,H wherein x is an integer of from 2 to 6 and y is an integer of from 1 to 10, and

2. at least one aldehyde having from 2 to 12, inclusive, carbon atoms.

2. A composition of claim 1 comprising a major proportion of a lubricating oil and from about 0.2 to about 30 weight percent of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of 90 to 270 SUS at 2 10F and a viscosity index of at least about and (b) us an adduct formed from tetraethylenepentamine and valeraldehyde.

3. A composition of claim 1 comprising a major proportion of a lubricating oil and from about 0.2 to about 30 weight percent of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of to 270 SUS at 210F and a viscosity index of at least about 85 and (b) is an adduct formed from tetraethylenepentamine and salicylaldehyde.

4. A composition of claim 1 comprising a major proportion of a lubricating oil and from about 0.2 to about 30 weight percent of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid 13 prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of 90 to 270 SUS at 2l0F and a viscosity index of at least about 85 and (b) is an adduct formed from tetraethylenepentamine and p-anisaldehyde.

5. An internal combustion engine fuel comprising hydrocarbons in the gasoline boiling range containing a small but effective amount, sufficient to impart increased detergency to said fuel, of an oil-soluble dispersant additive which is the reaction product obtained upon reacting a. a petroleum sulfonic acid with b. an adduct formed from l. at least one amine selected from primary monoamines having from 2 to 10, inclusive, carbon atoms, and polyamines represented by the formula H,N[(CH,),NH],,H wherein at is an integer of from 2 to 6 and y is an integer of from I to 10, and

2. at least one aldehyde having from 2 to l2, inclusive, carbon atoms.

6. A composition according to claim wherein the amount of said additive present in said motor fuel is in the range of 0.001 to 0.2 parts by weight additive per 100 parts by weight of gasoline.

7. A composition according to claim 5 which contains up to 5 ml tetraethyl lead per gallon.

8. An internal combustion engine fuel of claim 5 comprising a major proportion of hydrocarbons in the gasoline boiling range of 70-420F and from about 0.00] to 0.2 weight parts per I00 weight parts of gasoline of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of 90 to 270 SUS at 2l0F and a viscosity index of at least about 85 and (b) is an adduct formed from tetx'aethylenepentamine and valeraldehyde.

9. An internal combustion engine fuel of claim 5 comprising a major proportion of hydrocarbons in the gasoline boiling range of -420F and from about 0.00l to 0.2 weight parts per I00 weight parts of gasoline of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of 90 to 270 SUS at 0F and a viscosity index of at least about and (b) is an adduct formed from tetraethylenepentamine and salicylaldehyde.

10. An internal engine fuel of claim 5 comprising a major proportion of hydrocarbons in the gasoline boiling range of 70420F and from about 0.001 to 0.2 weight parts per 100 weight parts of gasoline of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of to 270 SUS at 210F and a viscosity index of at least about 85 and (b) is an adduct formed from tetraethylenepentamine and p-anisaldehyde.

Claims (14)

1. A LUBRICATING OIL COMPOSITION COMPRISING A MAJOR PROPORTION OF A LUBRICATING OIL CONTAINING A SMALL BUT EFFECTIVE AMOUNT, SUFFICIENT TO IMPART DECREASED DETERGENCY TO SAID LUBRICATING OIL, OF AN OIL-SOLUBLE DISPERSANT ADDITIVE WHICH IS THE REACTION PRODUCE OBTAINED UPON REACTING A. A PETROLEUM SULFONIC ACID WITH B. AN ADDUCT FORMED FOR
1. AT LEAST ONE AMINE SELECTED FROM PRIMARY MONOAMINES HAVING FROM 2 TO 10, INCLUSIVE CARBON ATOMS, AND POLYAMINES REPRESENTED BY TH FORMULA H2N ((CH2)XNH)YH WHEREIN X IS AN INTEGER OF FROM 2 TO 6 AND Y IS AN INTEGER OF FROM 1 TO 10, AND
2. AT LEAST ONE ALDEHYDE HAVING FROM 2 TO 12, INCLUSIVE, CARBON ATOMS.
2. at least one aldehyde having from 2 to 12, inclusive, carbon atoms.
2. A composition of claim 1 comprising a major proportion of a lubricating oil and from about 0.2 to about 30 weight percent of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of 90 to 270 SUS at 210*F and a viscosity index of at least about 85 and (b) us an adduct formed from tetraethylenepentamine and valeraldehyde.
2. at least one aldehyde having from 2 to 12, inclusive, carbon atoms.
3. A composition of claim 1 comprising a major proportion of a lubricating oil and from about 0.2 to about 30 weight percent of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of 90 to 270 SUS at 210*F and a viscosity index of at least about 85 and (b) is an adduct formed from tetraethylenepentamine and salicylaldehyde.
4. A composition of claim 1 comprising a major proportion of a lubricating oil and from about 0.2 to about 30 weight percent of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of 90 to 270 SUS at 210*F and a viscosity index of at least about 85 and (b) is an adduct formed from tetraethylenepentamine and p-anisaldehyde.
5. An internal combustion engine fuel comprising hydrocarbons in the gasoline boiling range containing a small but effective amount, sufficient to impart increased detergency to said fuel, of an oil-soluble dispersant additive which is the reaction product obtained upon reacting a. a petroleum sulfonic acid with b. an adduct formed from
6. A composition according to claim 5 wherein the amount of said additive present in said motor fuel is in the range of 0.001 to 0.2 parts by weight additive per 100 parts by weight of gasoline.
7. A composition according to claim 5 which contains up to 5 ml tetraethyl lead per gallon.
8. An internal combustion engine fuel of claim 5 comprising a major proportion of hydrocarbons in the gasoline boiling range of 70*-420*F and from about 0.001 to 0.2 weight parts per 100 weight parts of gasoline of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of 90 to 270 SUS at 210*F and a viscosity index of at least about 85 and (b) is an adduct formed from tetraethylenepentamine and valeraldehyde.
9. An internal combustion engine fuel of claim 5 comprising a major proportion of hydrocarbons in the gasoline boiling range of 70*- 420*F and from about 0.001 to 0.2 weight parts per 100 weight parts of gasoline of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of 90 to 270 SUS at 0*F and a viscosity index of at least about 85 and (b) is an adduct formed from tetraethylenepentamine and salicylaldehyde.
10. An internal engine fuel of claim 5 comprising a major proportion of hydrocarbons in the gasoline boiling range of 70*-420*F and from about 0.001 to 0.2 weight parts per 100 weight parts of gasoline of the reaction product obtained by the reaction wherein (a) is a petroleum sulfonic acid prepared by sulfonating a petroleum hydrocarbon fraction having a viscosity within the range of 90 to 270 SUS at 210*F and a viscosity index of at least about 85 and (b) is an adduct formed from tetraethylenepentamine and p-anisaldehyde.
US05503946 1974-09-06 1974-09-06 Additives for lubricants and motor fuels Expired - Lifetime US3919094A (en)

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US4131553A (en) * 1978-02-15 1978-12-26 Standard Oil Company (Indiana) Alkylbenzene sulfonic acid modified mannich reaction products from oxidized polymers
US4249912A (en) * 1978-04-27 1981-02-10 Phillips Petroleum Company Aminoamide fuel detergents
US4444567A (en) * 1982-07-01 1984-04-24 Phillips Petroleum Company Motor fuel composition containing an ashless antiknock agent
US4521319A (en) * 1981-03-13 1985-06-04 Chevron Research Company Dispersant lubricating oil additives
US5320767A (en) * 1993-02-22 1994-06-14 Exxon Research And Engineering Company Lubricant composition containing alkoxylated amine salt of hydrocarbylsulfonic acid
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US2831810A (en) * 1951-06-23 1958-04-22 Union Oil Co Detergent lubricating composition
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US4131553A (en) * 1978-02-15 1978-12-26 Standard Oil Company (Indiana) Alkylbenzene sulfonic acid modified mannich reaction products from oxidized polymers
US4249912A (en) * 1978-04-27 1981-02-10 Phillips Petroleum Company Aminoamide fuel detergents
US4521319A (en) * 1981-03-13 1985-06-04 Chevron Research Company Dispersant lubricating oil additives
US4444567A (en) * 1982-07-01 1984-04-24 Phillips Petroleum Company Motor fuel composition containing an ashless antiknock agent
US5320767A (en) * 1993-02-22 1994-06-14 Exxon Research And Engineering Company Lubricant composition containing alkoxylated amine salt of hydrocarbylsulfonic acid
WO2011033526A3 (en) * 2009-09-17 2011-11-24 Bharat Petroleum Corporation Limited Gasohol fuel composition for internal combustion engines
US9447343B2 (en) 2009-09-17 2016-09-20 Bharat Petroleum Corporation Limited Gasohol fuel composition for internal combustion engines

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