US3658707A

US3658707A - Fuel oil and lubricating oil compositions

Info

Publication number: US3658707A
Application number: US858505A
Authority: US
Inventors: David James Delafield; Alan H Edwards; Keith Owen
Original assignee: Exxon Research and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 1968-09-19
Filing date: 1969-09-16
Publication date: 1972-04-25
Anticipated expiration: 1989-04-25
Also published as: FR2018439A1; DE1946239B2; GB1241327A; DE1946239A1; JPS4945771B1; DK128688B; BE739045A; SE365815B; NL6914044A

Abstract

IMPROVED ANTICORROSION AGENTS FOR LUBRICATING OILS AND FUELS SUCH AS GASOLINE CONSISTING OF A MIXTURE OF (1) CARBOXYLIC ACIDS CONTAINING 10 TO 60 CARBON ATOMS PER MOLECULE, OR ESTERS OR ANHYDRIDES OF SUCH ACIDS AND (2) ESTERS OF ALKOXYLATED PHENOL-ALDEHYDE RESINS.

Description

United States Patent O U.S. Cl. 252--51.5 A 27 Claims ABSTRACT OF THE DISCLOSURE Improved anticorrosion agents for lubricating oils and fuels such as gasoline consisting of a mixture of (l) carboxylic acids containing to 60 carbon atoms per molecule, or esters or anhydrides of such acids and (2) esters of alkoxylated phenol-aldehyde resins.

This invention relates to fuel or lubricating oil compositions and in particular gasoline compositions.

Certain additives have been proposed for use in gasoline and other fuels which reduce corrosion and in the case of .gasoline act as anti-icing agents and carburettor detergents. Such additives have not however been completely successful when moisture is present in the fuel, since haze and emulsion problems can arise together with an unacceptable loss of the additive either into the aqueous phase or by adsorption onto tank or pipe line surfaces particularly when rust is present. Additives have also been proposed for use in lubricating oil compositions to reduce corrosion but frequently the pressure of such additives can further aggravate problems of emulsion formation When moisture is present particularly for example in steam turbine oils.

According to this invention improved fuel or oil compositions comprise a major proportion by weight of a fuel or lubricating oil and a minor proportion by weight of (A) (i) a mono or poly-carboxylic acid which contains 10 to 60 carbon atoms per molecule, or an anhydride or an ester of such an acid; or (ii) the reaction product of said acid, anhydride or ester with a hydroxy or an amino compound, and a minor proportion by weight of (B) an ester of an alkoxylated phenolaldehyde resin, (A) and (B) preferably being dissolved in a diluent or solvent.

Although the composition can contain any fuel, e.g. a kerosine, a gas oil, a distillate fuel such as a diesel fuel, an aviation jet fuel, the preferred fuel is a gasoline.

The gasoline can be a conventional gasoline for internal combustion engines, and these are supplied in a number of grades. lSuch gasolines may consist of mixtures of hydrocarbons of various types, including aromatics, olefins, paraifins, isoparafiins naphthenes and sometimes diolefins. The gasolines are derived from petroleum by refinnig processes such as fractional distillation, thermal cracking, steam cracking, catalytic cracking, catalytic reforming, polymerisation, hydroforming, alkylation and isomerization. Motor gasolines usually boil between 25 and 225 C. when tested by ASTM Method D86. Their (vapour pressures as determined by ASTM Method D323 are varied, depending on the season of the year during which they are to be used, from about 6 to about p.s.i. at 100 F. Their octane numbers as determined by ASTM Method D908 may range [from about 70 to 105 or higher.

Aviation gasolines are prepared by blending constituents similar to those found in motor gasolines but usually have narrower boiling ranges from about 37.5 C. to 165 C.

3,658,707 Patented Apr. 25, 1972 and somewhat more rigid specifications than do motor gasolines.

Suitable lubricating oils include animal, vegetable, or mineral oils, for example, petroleum oil fractions ranging from spindle oil to SAE 30, 40 or 50 lubricating oil grades; castor oil, fish oils, oxidised mineral oil or bright stocks. Synthetic esters may also be used, e.g. diesters such as those prepared by esterifying carboxylic acids such as adipic or sebacic acid with monohydride alcohols; or complex esters obtained by the esterification of a polyhydric alcohol (e.g. a polyglycol) with a dibasic acid (e.g. sebasic acid or adipic acid) and a monohydride alcohol (e.g. 2-ethyl-hexanol or a C oxo alcohol).

When additive (A) (i) is a monoor poly-carboxylic acid or an anhydride theerof it is preferably a compound represented by one of the following formulae wherein one of R and is a hydrocarbyl group containing 10 to 50 carbon atoms, and the other is either a hydrocarbyl group containing 10 to 50 carbon atoms, or hydrogen; X and Y are hydrogen atoms or hydrocarbyl groups and m is zero or an integer and n is zero or an integer. Of course R and must not be such that the total number of carbon atoms per molecule exceeds 60. In particular one of R and is preferably an alkyl or an alkenyl group containing 12 to 20 carbon atoms and X and Y are preferably hydrogen atoms, and m and n are each preferably integers of between 1 and 5. The groups R X and Y can be straight or branched chain, cyclic or acyclic, and although they may be aromatic they are preferably aliphatic.

Suitable examples of acid (1) are oleic acid, stearic acid, palmitic acid, and lauric acid.

As examples of acid (2) one may use polypropenyl, or polyisob-utenyl succinic acids, e.g. tetrapropenyl succinic acid.

Examples of anhydrides (3) and (4) include lauric anhydride and a polypropenyl succinic anhydride such as tetrapro penylsuccinic anhydride. Alternatively additive (A) (i) can be an ester of a monoor poly-carboxylic acid, and such esters include the esters of acids (1) and (2) described above. These esters are preferably derived from a low boiling alcohol e.g. one containing 1 to 5 car- HO (CXYh? Z1 2 Where X, Y and Z are hydrocarbyl groups or hydrogen atoms and m is zero or an integer and n is zero or an integer, and R is a hydrocarbyl group containing 1 to 50 carbon'atoms, or a hydrocarbyl group containing 1 to 50 carbon and also one or more ether linkages, or may be hydrogen if both m and n are integers. Preferably neither m nor n exceeds 5.

Particularly suitable alcohols are monohydric alcohols, e.g. those containing less than 20 carbon atoms per molecule, especially monohydric alcohols containing from 4 to 12. carbon atoms per molecule. Thus suitable alcohols from which additive (A) is derived include butanol-l, pentanol-l, isooctanol, isodecanol or dodecanol-l. If desired, however, the additive can be derived from a glycol, e.g., one containing 2 to 60 carbon atoms, for example ethylene glycol, butylene glycols, pinacone, tetramethylene glycol etc. in which case one mole of glycol reacts with two moles of acid or anhydride.

Aromatic alcohols, e.g. benzyl alcohol, toluyl alcohol, may also be used; as may phenolic compounds, such as phenol itself, the cresols, xylols or catechol.

Another suitable class of mono-hydroxy compounds are ether-alcohols which are for example obtained by reacting aliphatic alcohols with an alkylene oxide. Suitable ether alcohols contain for example 2 to 40 carbon atoms per molecule, and include methoXy-methanol, ethoxy butanol, or ethoxyethanol.

Suitable amino compounds include p-, sor t-monoamines, diamines, polyamines, or hydroxyamino compounds.

Suitable amino compounds from which additive (A) (ii) may be derived include amines of the formulae where R R and R are alkyl, alkaryl or alkenyl groups containing 1 to 200 carbon atoms, or hydroxy or amino substituted alkyl or alkaryl groups containing 1 to 200 carbon atoms, or hydrogen atoms.

When reacted with a monocarboxylic acid, amides or salts of the following formulae are formed where R is as defined previously. At least one of the groups R R R and R should contain at least carbon, atoms, particularly between 12 and 20 carbon atoms.

Suitable nonamines are those of the formula R NH R3R4NH 0r R3R4R5N Where R3, R4 and R5 BIC hydrocarbyl or substituted hydrocarbyl e.g. alkyl, cyclo alkyl, aryl, alkenyl, substituted aryl or heterocyclic radicals. Thus, the groups R R or R can be for example octyl, nonyl, decyl, undecyl, pentadecyl, hexadecyl, octadecyl, eicosyl, octadecenyl, or octadecadienyl.

The groups R R and R can vary widely, and may for example contain from 1 to 30 carbon atoms, preferably 8-22 carbon atoms.

Aromatic monoamines include aniline, substituted anilines, benzylamine and naphthylamine. Suitable heterocyclic amines include furyl amine, piperidine and N-vinyl pyrrolidone.

Suitable polyamines which can be used include aliphatic polyamines, and heterocyclic polyamines. The preferred polyamines are alkylene polyamines, and hydroxy alkylene polyamines.

Thus, suitable polyalkylene polyamines are those compounds having the formula H N(RNH H where R is an alkylene radical or a hydrocarbyl substituted alkylene radical and y is an integer. Thus, suitable polyamines are diethylene triamine, triethylene tetramine, or tetra-ethylene pentarnine.

The hydroxyamino compounds which may be used include monohydroxyamines of the formula R4 R3'I IR6OH dihydroxyamines of the formula R OH R1011 or trihydroxyamines of the formula HO-RuN where R and R are hydrogen or hydrocarbyl groups and R R and R are divalent hydrocarbon, e.g. alkylene groups.

Thus, the groups R and R may be alkenyl, alkyl, cycloalkyl, or phenyl groups and the groups R R and R may be alkylene groups of the formula z). where x is preferably a whole number from 1 to 8.

In general the hydroxyamino compounds should preferably contain from 1 to 40 carbon atoms.

Particularly suitable are monoalkanolamines, especially where the nitrogen atom is substituted by alkyl groups, e.g. monoalkanolamines of the formula N n 0H where R and R are alkyl groups, e.g. C to C alkyl groups and R is an alkylene group, e.g. a C to C alkylene group. Thus, one may use N,N diethyl ethanolamine or N,N dibutyl hexanolarnine.

Also suitable are monoalkanolamines in which one or more of the alkyl groups also contains an amino substituent, i.e. amino alkyl monoalkanolamines, e.g. amino ethyl ethanolamine, amino propyl ethanolamine, amino propyl butanolamine, etc. One may of course use analogous amino alkyl dialkanolamines, e.g. N-amino ethyl diethanolamine.

The additive (A) (ii) is preferably the reaction product of a hydroxy or an amino compound with a succinic acid, anhydride or ester which has been substituted by one or more hydrocarbyl groups. Particularly suitable hydrocarbyl groups are alkenyl or alkyl groups, e.g. those containing from 3 to 55 carbon atoms, especially 10 to 40 carbon atoms.

Thus, the substituted succinic acid can be represented by the general formula where one of R and R is hydrogen, and the other is an alkenyl group. The alkenyl group can be straight-chain or branched chain and is preferably derived from a polyolefin, e.g. polypropenyl, polyisobutenyl or polypentenyl, and preferably of MW 50 to 600. Instead of being substituted by a hydrocarbyl group this substituent group can be a hydrocarbyl group which itself is substituted by a small proportion (e.g. less than 10%) of other atoms or groups, e. g. halogen atoms or nitro groups.

The corresponding anhydride, or ester can also be used. If an ester, it is preferably derived from a low boiling alcohol, e.g. one containing 1 to carbon atoms per molecule. Thus, the methyl, ethyl, propyl, butyl or pentyl esters should preferably be used.

One of the preferred additives (A) (ii) for use in the fuel compositions of this invention are esters represented by the formula 0 ca c 1 a \m where either one of the groups R and R is an alkenyl group containing from 8 to 40 carbon atoms and the other of the groups R and R is a hydrogen atom, and R is C to C alkyl group, or the group wherein R and R are C; to C alkyl groups and R is a C to C alkylene group, the total number of carbon atoms in the groups R R and R being from 4 to 12.

The mono-ester may conveniently be prepared by reaction of equimolar proportions of the substituted succinic acid or its anhydride with a mono-hydroxy compound. Usually simple admixture is suflicient, but when reacting a hydroxyamine with the substituted anhydride heating may be necessary.

Depending on the reactants used and the quantities used therefore, additive (A) (ii) can be a mono-, di-, or polyester, or an amide, or an amidine.

If desired additive (A) (ii) can be an ammonium or amine salt of the reaction product between an amino or hydroxy compound and a monoor poly-carboxylic acid, the anhydride thereof, of the ester thereof (e.g. a substituted succinic acid, anhydride or ester). Of course, there must be at least one free carboxylic group or phenolic hydroxy group present for the salt to be formed.

Other particularly preferred additives (A)(ii) are the reaction products of a fatty acid (e.g. oleic acid, linoleic and stearic acid) and an amino alkyl monoalkanolamine, (e.g. amino ethyl ethanolamine, or amino propyl propanolamine).

If desired the fuel or oil compositions of this invention may include mixtures of two or more of the above described additives (A) (i) and/or (A) (ii).

The phenol from which the ester of an alkoxylated phenolaldehyde resin (B) is derived may contain a substituent such as a hydrocarbyl or a substituted hydrocarbyl group or an acyl group. This substituent may be in the para position with respect to the phenolic group, but can however be in the metaor ortho positions. Substituted hydrocarbyl groups may be hydrocarbyl groups substituted with, for example, halogen atoms. Preferably the hydrocarbyl group is unsubstituted. This hydrocarbyl group can be an alkyl group, e.g. a branched chain alkyl group, but can also be, for example, an alkenyl group. Particularly suitable substituted or unsubstituted hydrocarbon groups are those containing between 1 and 30 carbon atoms, e.g. methyl, t-butyl, hexyl, decyl, tetradecyl, octadecyl or stearyl, eicosyl, tetracosyl, hexacosyl or mixtures of these groups.

In preparing the phenol-aldehyde resin the phenol is condensed with an aldehyde. The aldehyde is preferably formaldehyde, or para formaldehyde but other aldehydes, especially those containing not more than 25, e.g. less than 8 carbon atoms per molecule could be used instead, e.g. acetaldehyde, butyraldehyde, benzaldehyde, or propionaldehyde. Furfuraldehyde may also be employed.

The phenol-aldehyde resin from which the ester is prepared may be prepared by methods well known in the art.

When the phenol-aldehyde resin is derived from phenol itself, a particularly suitable method of preparation is that given in Preparative Methods of Polymer Chemistry, Interscience Publishers Inc., New York by Sorenson and Campbell, p. 295 (1961 ed.) i.e. heating together phenol and aldehyde in the presence of an acid catalyst. When reacting phenol with the aldehyde it is preferred that O.6O.95 moles of aldehyde be employed to every mole of phenol.

In order to alkoxylate the phenol-aldehyde resin thus obtained one reacts the resin with an-alkylene oxide. Preferably the alkylene oxide contains not more than 4 carbon atoms per molecule, e.g. ethylene oxide, propylene oxide or butylene oxide.

The resin may be reacted with the alkylene oxide in the presence of a catalyst, e.g. an alkaline catalyst such as sodium acetate, sodium hydroxide or sodium 'methvl ate. The amount of alkaline catalyst may be small, e.g. between 0.1% and 2% by weight. The reaction may take place under pressure, e.g. up to pressures of 20 atmospheres, and the reaction temperature may be as high as 200 C. The alkoxylation is conveniently carried out in the presence of an inert solvent, e.g. xylene, Decalin, or diethyl ether. Usually the quantity of alkylene oxide reacted is from 1 to 2 moles per hydroxyl radical in the resin.

Finally, to prepare the ester (B) the alkoxylated phenolaldehyde resin is reacted with a carboxylic acid, or a derivative thereof, preferably a mono-carboxylic acid. Especially suitable are mono-carboxylic acids containing between 8 and 32 carbon atoms per molecule, e.g. the higher fatty acids. Thus, saturated fatty acids include lauuric acid, myristic acid, palmitic acid and stearic acid; whilst unsaturated fatty acids include oleic acid, linoleic acid and linolenic acid. One may of course use a mixture of acids, e.g. mixed fatty acids such as the fatty acids obtained from the hydrolysis of cottonseed oil, or soyabean oil.

Instead of reacting the alkoxylated resin with a carboxylic acid one can use, for example, the corresponding acyl chloride or anhydride; or in some cases one may employ transesterification.

.Generally one reacts about one equivalent of carboxylic acid per hydroxy group in the resin.

Additive (B) may if desired also incorporate a homopolymer of an alkylene oxide (e.g. ethylene oxide, propylene oxide) or a copolymer of a mixture of alkylene oxides (e.g. ethylene oxide and propylene oxide), formed by reaction with an alkanolamine such as methanolarnine, a dialkanolamine such as dipropanolamine. The production of such polymers is known to the art; see, for example, US. Pat. 1,923,178. Such a polymer is simply mixed with the ester of the alkoxylated phenol-aldehyde resin.

The additives (A) and (B) may if desired be dissolved in a diluent, e.g. toluene, kerosine or xylene. The concentration may be, for example, around 25 to 75 wt. percent, e.g. 50 Wt. percent.

Suitable quantities of additives (A) and (B) are 0.00005 wt. percent to 0.025 wt. percent e.g. about 0.0025 wt. percent of (A) and 0.000005 to 0.025 wt. percent e.g. about 0.0005 wt. percent of (B) based on the total weight of the fuel composition. For oils, suitable quantities are for example 0.005 wt. percent to 0.5 wt. percent, particularly 0.015 to 0.03 wt. percent of (A) and 0.005 to 0.5 wt. percent, particularly 0.025 to 0.25 wt. percent of (B), based on the total weight of the oil composition.

The fuel may also incorporate other additives. Thus, gasoline, may also contain anti-knock agents, e.g. tetra ethyl lead, halohydrocarbon scavengers, e.g. ethylene dibromide or ethylene dichloride, or deposit modifiers, e.g.

organic esters of oxy acids of phosphorus, or antioxidants e.g. 2,4-dimethyl-6-t-butyl phenol and N,N di sec butyl para phenylene diamine.

EXAMPLE 1 Preparation of Additive (A).-Equimolar quantities of tetra propenyl succinic anhydride and NN' diethyl ethanolamine were stirred together with 50% wt. of kerosine diluent at ambient temperature.

Preparation of Additive (B).-Slightly less than molar quantities of para-formaldehyde were reacted with p-tbutyl phenol at about 385 F. in a heavy aromatic naphtha solvent system. After the reaction was completed the solvent was adjusted to give a solution containing about 50 wt. percent phenol-HCHO resin, the resin then being neutralised with excess NaOH. The solution was then ethoxylated by reacting with ethylene oxide (1.6 gm. oxide per 1 gm. of resin solution). After neutralisation with naphthenic acid and adjustment of the pH to about 2 to 3 with dodecyl benzene sulphonic acid the ethyoxylated resin solution was reacted with palmitic acid to form the ester. 7

The ester was then mixed with about /3 its weight of copolymer of ethylene oxide and propylene oxide with diethanolamine having a MW of about 4000 to 5000. This mixture was then diluted about 50% with a heavy aromatic naphtha solvent to give additive (B).

A gasoline composition was prepared by adding to gasoline 0.0001 wt. percent of additive (A') and 0.0001 wt. percent of additive (B'). The advantages of this composition over gasoline compositions containing only (A') (B) are indicated by the following test procedure.

Test Procedure 250 mls. of gasoline were stirred gently by magnetic stirrer with 10 mls. of deionised water in a 1000 ml. glass cylinder. A mild steel specimen was suspended in the mixture on one of two copper coated steel rods Which were immersed parallel to each other, but not in contact with each other. The appearance of the steel specimen was inspected at regular intervals to assess the amount of resting formed.

Results Percent wt. add.

Additive in gasoline Observations of steel specimen Additive A lttuslt3 appeared during 6th day. Additive B 2 0.

Additive A 0001 Rust appeared during 10th day. Additive B 0001 Do.

EXAMPLE 2 Percent w. add. Observations of Additive in gasoline steel specimen Additive A 0, 0015 B17150 appeared after ays. Additive B 0. 0015 Rust appeared after 8 days. Add tive A. 0. 00075 }No rusting appeared Additive B 0. 00075 after 14 days.

EXAMPLE 3 Equimolar quantities of tetrapropenyl succinic anhydride and n-octanol were refluxed in toluene for 3 hours in the presence of a trace of tri-ethylamine. The solution obtained was used as additive C.

Gasoline compositions were prepared having the following compositions Percent area rusted Number of days exposed. 1 2 3 4 Gasoline itself 50 Composition (1) Nil Trace Trace Composition (2) Nil Trace Trace 10 Composition (3) 5 5 10 10 Thus, it can be seen that minimum rusting takes place when gasoline compositions of the invention (compositions 1 and 2) are used.

What is claimed is:

1. An oil composition comprising a major proportion by weight of an oil selected from the group consisting of a fuel oil and a lubricating oil and a minor proportion by Weight in an amount suflicient to inhibit corrosion of a mixture comprising:

Additive A, which is selected from the group consisting of monoand poly-carboxylic acids which contain 10 to 60 carbon atoms per molecule, anhydrides of such acids and monoor polyesters of such acids; monoor polyamides and amino salts of such acids and mixtures thereof; said esters being derived from a hydroxy compound of the formula where X, Y and Z are hydrocarbyl groups or hydrogen atoms and m is zero or an integer, and n is zero or an integer, and R is a hydrocarbyl group containing 1 to 50 carbon atoms, or a hydrocarbyl group containing 1 to 50 carbon atoms and one or more ether linkages, or hydrogen when both m and n are integers, or hydroxyamine of the formula where R and R are hydrogen or hydrocarbyl groups, and R R and R are divalent hydrocarbon groups; said amides being derived from an amine chosen from the group consisting of (i) monoamines (ii) aromatic monoamines (iii) aliphatic polyamines (iv) hydroxy alkylene polyamines (v) heterocyclic polyamines; or said hydroxyamine and said amino salt being derived from said amine or said hydroxyamine; and Additive (B) which is a carboxylic acid ester of an alkoxylated phenol-aldehyde resin wherein said alkoxyl group contains 1 to 30 carbon atoms and said aldehyde contains 1 to 25 carbon atoms; and the proportion by weight of A to B ranges from 500:1 to 1:500 when in said fuel and from 100:1 to 1:100 when in said lubricating oil.

2. A composition as claimed in claim 1 wherein the fuel is a gasoline.

3. A composition as claimed in claim 1 wherein additive (B) is derived from a phenol substituted with a hydrocarbyl group.

4. A composition as claimed in claim 3 wherein the hydrocarbyl group contains between 1 and 30 carbon atoms.

5. A composition as claimed in claim 1 wherein the aldehyde is formaldehyde or para formaldehyde.

6. A composition as claimed in claim 1 wherein additive (B) is derived from an alkylene oxide containing not more than 4 carbon atoms per molecule.

7. A composition as claimed in claim 1 wherein additive ('B) is derived from a mono-carboxylic acid having between 8 and 32 carbon atoms per molecule.

8. A composition as claimed in claim 1 wherein Additive (B) also incorporates a homopolymer of an alkylene oxide or a copolymer of alkylene oxides, said homoor copolymer containing the residue of an alkanolor dial kanolamine.

9. A composition as claimed in claim 1 wherein Additive A is selected from the group consisting of:

where one of R and is a hydrocarbyl group containing 10 to 50 carbon atoms, and the other is either a hydrocarbyl group containing 10 to 50 carbon atoms, or hydrogen.

10. A composition as claimed in claim 9 wherein m and n are each integers of between 1 and 5.

11. A composition as claimed in claim 10 wherein the acid or anhydride is selected from the group consisting of polypropenyl and polyisobutenyl succinic acids and a polypropenyl succinic anhydride.

12. A composition as claimed in claim 1 wherein additive (A) is derived from a monohydric alcohol containing from 4 to 12 carbon atoms per molecule.

13. A composition as claimed in claim 1 wherein Additive (A) is derived from said hydroxy compound.

14. A composition as claimed in claim 13 wherein neither in nor n exceeds 15. A composition as claimed in claim 1 wherein additive (A) is derived from said monoamine selected from the group consisting of amines of the formulae R NH R R NH and R R R N where R R and R are hydrocarbyl or substituted hydrocarbyl.

16. A composition as claimed in claim 1 wherein additive (A) is derived from said polyalkylene polyarnine having the formula =I-I N('RNH I-I where R is an alkylene radical or a hydrocarbyl substituted alkylene radical.

17. A composition as claimed in claim 1 wherein Additive (A) is derived from said hydroxyamine.

18. A composition as claimed in claim 17 wherein additive (A) is derived from a monoalkanolamine where R and R are C to C alkyl groups and R is a C to C alkylene group.

19. A composition as claimed in claim 1 wherein Additive (A) is derived from said monoamine of the formula where R R and R are alkyl, alkaryl or alkenyl groups containing 1 to 200 carbon atoms, or hydroxy or amino substituted alkyl or alkaryl groups containing 1 to 200 carbon atoms, or hydrogen atoms.

20. A composition as claimed in claim 1 wherein additive (A) is derived from a monoalkanolamine in which one or more of the alkyl groups also contains an amino substituent.

21. A composition as claimed in claim 20 wherein the amino alkyl monoalkanolamine is selected from the group consisting of aminoethyl ethanolamine, amino propyl ethanolamine, and amino propyl butanolamine.

22. A composition as claimed in claim 1 wherein Additive (A) contains an acid portion derived from a succinic acid, anhydride or ester which has been substituted by one or more hydrocarbyl groups.

23. A composition as claimed in claim 22 wherein the hydrocarbyl group is selected from the groups consisting of alkenyl and alkyl groups containing from 10 to 40 carbon atoms.

24. A composition as claimed in claim 23 wherein the alkenyl group has a MW of between 50 and 600..

25. A composition as claimed in claim 1 wherein additive (A) is an ester represented by the formula Il -CH iii-ca where either one of the groups R and is an alkenyl group containing from 8 to 40 carbon atoms, and the other of the groups R, and

i is hydrogen, and R is a C to C alkyl group, or the group wherein R and R are C to C alkyl groups and R is a C to C alkylene group, the total number of carbon carbon atoms in the groups R R and R being from 4 to 12.

26. A composition as claimed in claim 1 wherein Additive (A) is derived from a fatty acid and said hydroxyamine, said hydroxyamine being an amino alkyl monoal-kanolamine.

27. A composition as claimed in claim 26 wherein the fatty acid is selected from acids consisting of oleic acid, linoleic acid and stearic acid.

References Cited UNITED STATES PATENTS 2,334,158 11/1943 Von Fuchs et al. 252-56 R 2,498,195 2/1950 Ballard et al. 252--51.5 R 2,718,503 9/1955 Rocchini 25251.5 A 2,939,842 6/1960 Thompson 44-62 X 3,448,049 6/1969 Preuss et al 252-5 1.5 A

DANIEL E. WYMAN, Primary Examiner W. J. SHINE, Assistant Examiner US. Cl. X.R.