US 3340191 A
Abstract available in
Claims available in
Description (OCR text may contain errors)
United States Patent 3,340,191 FUEL AND LUBRICANT COMPOSITIONS Harry J. White, Riverside, and Richard C. Mansfield, Cherry Hill, N.J., assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Filed Dec. 5, 1963, Ser. No. 326,658 11 Claims. (Cl. 25249.8)
This application is a continuation-in-part of application Ser. No. 245,379, filed Dec. 18, 1962, now abandoned.
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.
The present compositions are produced by incorporating into a fuel or lubricant base at least one of the following pairs of compounds:
In the above formulas, 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.
In the above-listed compounds, 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,
. ethyl, butyl, isohexyl, tertiary-octyl, nonyl, decyl, dodecyl,
tertiary-decyl and tertiary-octadecyl. 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.
The various 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
(Ila) R 0 onion?) yon R (OCHzCHz)zOH as desired.
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.
In order to assure highest yields of desired secondary and tertiary phosphate ester, it is necessary to use three moles of the alcohol to one mole of the phosphorous oxychloride. It is also preferred to employ a slight excess of the alcohol over the required 3:1 ratio in order to assure that a product of desired composition is obtained. Molecular ratios of up to 3.5 :1 of the alcohol to phosphorous oxychloride are useful and desirable. The excess amount of the alcohol need not be separated from the secondary and tertiary phosphate ester product since desirable results for the purposes of the present invention are obtained when the phosphate ester product contains a minor amount of excess alcohol of the types defined hereinbefore. There also may be produced small amounts of the chloride of the reactants (Ia), (Ila) or (Illa), as the case may be. This minor amount of chloride also need not be separated from the phosphorus-containing product since it does not alter the valuable results of the present invention.
It is desirable to employ a 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. If desired, 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. In the preferred process, 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.
The system is then heated while 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.
The 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. For lubricant formulations, 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. In fuels, the range is 0.001% to 0.1%, preferably 0.005% to 0.05 by weight. The compounds of the present invention with their rigidly restricted secondary and tertiary phosphate ester structures and proportions possess a surprisingly advantageous combination of the desired properties of solubility in the oils and fuels contemplated, subtantial insolubility in water and a high degree of effectiveness as anti-rust, anti-stalling, detergency, dispersing and ignition control additives. 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.
As will be clearly understood in the art, the 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. In this test, the base fuel resulted in nine stalls. When one of the compounds (I), (II), and (III) was employed in the samebase fuel to produce a composition of the present invention, the number of stalls was significantly reduced. Outstanding in this respect is the pair of compounds:
which reduced the stalls to five. In this test, there is employed 0.02% by weight of the additives tested, which is a commercially employed amount.
The 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:
Commercially acceptable additives'for anti-rust are employed in amounts of about 0.01% by weight.
The compositions of the present invention were evalu .ated in a standard carburetor detergency test. In this evaluation there was employed a 1954 model, 6-cylinder Plymouth 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. There was then incorporated into the same base fuel one of the pairs'of secondary and tertiary phosphate esters in order to provide a composition of this invention. The test was then continued for an additional five hours. Theevaluation .was based on the percent clean-up of the black deposit. Commercially available compositions 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:
The 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. In 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. 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:
Outstanding performers were the first four pairs in the above list, which gave results below 20 mg. of sludge accumulation even when employed in amounts of as little as 0.005% and less.
The 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.
In this test, commercially acceptable additives in amounts of 1% by weight in a base oil led to sludge accumulations of from 25 to 50* mg. The compositions of the present invention led to results in the commercially acceptable range and many were such effective detergents and dispersants that accumulations of below 25 mg. were obtained. Particularly outstanding in this respect were the pairs:
in the 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.
A mixture of this material and 10% by weight of water is stirred and heated to reflux during one hour, refluxed for two hours at C. and stripped free of water during two hours at 100 to C. at 20 to 25 mm. Hg. The product then has an acid number of 13.2 and a hydrolyzable acid number of 13.4 and is identified as follows in weight percent:
[CvH19Ct 4(O CH2OH2)5O]3P=O 55 OH [C9H10CdH4(O CHzOHz)50]zl =O 22 C9H19C5H4 OCH2CHZ)5OH 14 CuH19CsH4 O CH2CH2)5C1 9 Example 2 A mixture of 400 parts of toluene and 138 parts (0.345 mole) of the adduct of 4 moles of ethylene oxide and nonylphenol is refluxed for one hour while any water present is removed by means of an attached water separator. 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 have the formulas:
[C9H19C6H4(O CH2CH2)4O]ZP=O (H-1 [Co iOsH4(OCHzCH2)4O]zP=O 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:
[(CaH1v)2CtHa(O OHZCH2)9013P=O and and
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:
To 235 parts (0.345 mole) of an ethylene oxide adduct of dinonylphenol having an average of seven oxyethylene groups added to each mole of dinonylphenol is added 15.3 parts (0.10 mole) of phosphorus oxychloride over a period of hour with stirring and cooling to maintain the mixture at to C. The mixture is then stirred for /2 hour while the temperature is raised to 25 C. A vacuum line is attached and the pressure is reduced to to 30 mm. Hg. The mixture is heated to 100 C. during 1% hours and stirred at 100 to 110 C. at 20 to 30 mm.
8 Hg for 4 /2 hours while hydrogen chloride is removed. The product is cooled and analyzed. 7
The phosphorous ester products have the formulas:
[(Csz 1v)zCs 3( 2C 2)10laP= 11 [(CnH1n)2CsHa(OCH2CHz)1O]nP=O Example 7 To 112 parts (0.230 mole) of the adduct of 6 moles of ethylene oxide to nonylphenol is added with stirring 10.2 parts (0.066 mole) of phosphorous oxychloride at 10 to 15 C. The mixture is then stirred for /2 hour while the temperature is raised to 25 C. The pressure is reduced to 10 to 20 mm. Hg and the mixture is heated to C. during 1% hours and maintained at 100 to C. at 10 to 20 mm. Hg for 4 /2 hours while hydrogen chloride is removed. The product is cooled and analyzed. The phosphorous ester products are:
To a stirred mixture of parts (0.345 mole) of the adduct of 3.8 moles of ethylene oxide to dodecylphenol and 33 parts (0.34 mole) of triethylamine is added during one hour at 50 to 55 C., 15.3 parts (0.10 mole) of phosphorous oxychloride. The mixture is stirred another two hours at 50 to 55 C., filtered, diluted with 1.5 parts of a C C tertiary alkyl primary amine, stirred for /2 hour at 30 to 60 C. and then for another /2 hours at 30 to 60 C. at 10 to 50 mm. Hg. The phosphorous ester products are:
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.
of aliphatic alcohols containing 1% to 5% of myristyl alcohol, 30% to 39% of cetyl alcohol and 60% to 68% of stearyl alcohol and 21 parts (0.21 mole) of triethylamine is added during 1%. hour, 10.2 parts (0.067 mole) of phosphorous oxychloride While the temperature is maintained below 55 C. The mixture is stirred three hours at 50 to 55 C. and filtered free of triethylamine hydrochloride. The products are represented by the following formulas:
In the above Examples 2 to 9, inclusive, the final step in the reaction, in each instance, 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;
1. 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:
i: (OCH2CHz) O:| 1 =o and R! ?H @w-on-omn-o] P=O 10 R3 If:
[R (O-GHz-CHz)z-O]3P=O and I on [RrQ-(O-CHr-OHQ .-0 21 =o R3 I ls in which:
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 and 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. 2. A composition according to claim 1 in which said member is a mixture of:
[C9 19Ce 4( C 2C :)4O]sP=O on [C9H19C5H4(OCH2CH2)-1O]2P=O 3. A composition according to claim 1 in which said member is a mixture of:
[(CnHm)2CaHa(O CH2CH2)9O]3P=O on [(CoH1n)2CsH3(OCH2CH2)9O]2P=O 4. A composition according to claim 1 in which said member is a mixture of:
6. A composition according to claim 1 in which said member is a mixture of:
8; A normally liquid hydrocarbon fuel containing from 0.001% to 0.1% by weight of a mixture of:
9. A normally liquid hydrocarbon fuel containing from 0.001% to 0.1% by weight of a mixture of:
10. A normally liquid hydrocarbon fuel containing from 0.001% to 0.1% by Weight of a mixture of:
11. A lubricant containing from 0.1% to 10.0% by weight of a mixture of:
[G9H1BC6H4(OCH2C 2)JO]2P=O References Cited UNITED STATES PATENTS 2,723,237 11/1955 Ferrin 252-498 2,930,680 3/1960 Smith et a1. 44-76 X 2,959,473 11/ 1960 Andress 44-69 2,999,740 9/ 1961 Banigan 44-76 X 3,000,824 9/1961 Morway et a1. 252-498 X 3,004,056 10/ 1961 Nunn et al.
3,009,790 11/1961 Pellegrini et a1. 44-76 X 7 3,033,889 5/1962 Chiddix 44-76 X FOREIGN PATENTS 653,353 5/1961 Great Britain. 663,557 12/ 1951 Great Britain.
DANIEL E. WYMAN, Primary Examiner.
P. P. GARVIN, Assistant Examiner.