US3484375A - Lubricating oils and fuels containing organic phosphite reaction products - Google Patents

Description

United States Patent 3,484,375 LUBRICATING OILS AND FUELS CONTAINING ORGANIC PHOSPHITE REACTION PRODUCTS Shih-En Hu, Roselle, Union, N.J., assignor to Esso Research and Engineering Company, a corporation of Delaware N0 Drawing. Filed Dec. 30, 1966, Ser. No. 606,042 Int. Cl. Crn 1/46; C101 1/26 US. Cl. 252--49.9 7 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to the production of novel additives for lubricating oils, middle distillate fuels, residual fuels or reduced crudes in order to improve their resistance to oxidation, sludge formation, to improve their viscosity index, or to improve their flowability and pour point characteristics. Such reaction products have been found to be particularly useful as additives as aforementioned since they tend to minimize sludge formation, bearing wear, and also tend to act as dispersants for any sludge that is formed and to the extent that it is formed. They are useful not only in lubricating oils but also in fuels because it has been found that they have a certain degree of fiowability improvement of the fuel under low ambient temperatures and, at the same time, minimize wear on pumps which are used to transport the fuel. Likewise these novel additives tend to minimize fouling and plugging difliculties in the transportation of fuels through pipes and the like by means of pumps.

Various phosphite derivatives have, in the past, been produced and used as additives in both hydrocarbon fuel compositions and in lubricating oil compositions for much the same purposes as are hereinbefore described. Usually, however, they suffer from one or more deficiencies with respect to these characteristics and efforts are being constantly made to find novel additives which will impart improved desired characteristics in one or more respects to such hydrocarbon liquids when added thereto, or which will serve a combination of functions for improving several desired characteristics when added to such hydrocarbon liquids. High operating temperatures in internal combustion engines tend to accelerate the detrimental oxidative influences on lubricating oils and this, in turn, tends to result in the premature breakdown of these oils with the resultant formation of acids and other sludgetype materials which generally gum up, clog, and corrode bearings and deposit on internal surfaces, thus leading to excessive wear of bearing surfaces and plugging difiiculties in oil circulation systems because of the excessive quantities of sludge formed. It is recognized that sludge formation, whether or not the sludge is deposited, is an undesirable phenomenon associated with the use of lubricating oils and is to be minimized or avoided altogether, if it is possible to do so.

The novel organic phosphite reaction products hereinafter described are ashless in nature which means that they tend to eliminate the formation of deposits on the internal surfaces of internal combustion engines when added to lubricating oils contained in these engines, whereice as, sludge dispersants and sludge inhibitors containing metal ions, upon their breakdown, tend to deposit the metals in one form or another on the internal surfaces of such engines, that is, they leave a residue or ash-forming deposit which is undesirable. Again, some of the heretofore used sludge inhibitors and sludge dispersants tend to be too corrosive for practical purposes toward the conventionally used copper-lead bearings customarily employed in automotive and diesel engines. The heretofore employed dispersants may exhibit certain desirable properties but they may lack sufficient antioxidant and antiwear properties thus making it necessary to employ still other additives in addition to the dispersants and antioxidants in order to impart additional desirable properties to the fuels and lubricating oils. The novel organic phosphite reaction products are designed to impart the anti oxidant, rust preventive, sludge inhibiting and sludge dispersing characteristics desired in lubricating oils and fuels, as they are presently employed and handled, to a greater degree than has heretofore been thought possible.

The novel products are produced by reacting organic phosphite monoor di-esters containing two or one hydroxyl groups attached to the phosphorus with an alkylene polyamine, or an amino alcohol in liquid phase and at elevated or superatmospheric temperature for a sufficient length of time to effect a condensation of the said phosphite with the amino group or groups present in the second reactant. There is some indication that, under the circumstances obtaining, a polymerization takes place along with the condensation reaction but it is not intended that the invention be limited to this concept. Also, organic phosphite halo-, monoor di-esters may be reacted with an alkylene polyol to yield essentially the same type of condensation products, with hydrogen halide being split off instead of water.

One of the principal types of phosphite ester reactant employed is prepared by the esterification reaction of an alcohol with a phosphorous trihalide such as phosphor ous trichloride of phosphorous tribromide. Depending upon the relative number of moles of alcohol employed, the ester will be a mono-, di-, or triester or a mixture of two or more of these esters. It is preferred to employ the monoand di-esters or mixtures thereof. It is also desirable, prior to reaction of the phosphite mono-, dior tri-ester with the amino-containing reactant, that the ester be partially hydrolyzed with water or steam so as to either drive off the unreacted halogen from the phosphorous trihalide remaining by reason of the use of the phosphorous trihalide reactant or to hydrolyze ofl? one or two ester groups if a dior tri-ester is employed. It is not necessary that the phosphite triester be partially hydrolyzed before reaction with the polyamine or the amino alcohol since a direct reaction between these two types of reactants can be accomplished by simple heating of their admixture to moderately elevated, i.e., superatmospheric, temperatures. However, better yields of the reaction products are obtained, if the phosphite dior tri-ester is first partially hydrolyzed so that it contains one or two hydroxyl groups attached directly to the phosphorus atom in each molecule and thereafter the hydrolyzed ester is reacted with the polyamine or the amino alcohol.

The formation of the novel phosphorus condensation products is also readily effected, under the same reaction conditions as those employed, by employing as reactants, the phosphite monoor di-esters as heretofore described and in which the remaining phosphorous valence is taken up with a halogen such as chlorine or bromine; or the mono ester may contain two chlorines or bromines. Such reactants are employed, however, only when employing the alkylene polyols as the second reactant, in which case hydrogen halide is evolved.

It is not necessary that the organic phosphite be an ester for, as will be shown by the later more detailed description, a condensation effected by means of a Friedel- Crafts type catalyst such as aluminum chloride or aluminum bromide may effectuate a reaction in which the union of the phosphorus atom of a phosphorous trihalide directly to the nucleus of an alkyl substituted aromatic hydrdocarbon is accomplished in the form of either a monoaryl, diaryl or triaryl bonding to the phosphorus atom depending again upon the number of moles of reactants employed per mole of phosphorous reactant.

Insofar as the reactant phosphite esters are concerned, they may be represented by the general formula wherein: R is a hydrocarbon radical selected from the group consisting of alkyl, chloralkyl, aryl, chloraryl, alkaryl, chloralkaryl, cycloalkyl, chlorcyclo alkyl, alkenyl, chloralkenyl, aralkyl, and chloraralkyl; and R and R are hydrogen or the same as R provided further that R or R is hydrogen where the reaction involves a polyamine or an amino alcohol, and R and/ or 0R are halogen, where the reaction involves a polyol.

Specific reactant phosphites which are useful as reactants after esterification are shown in their ester form only by the following. The mono-, di-, or tri-esters whose mono esters are as follows:

methyl phosphite ethyl phosphite n-propyl phosphite isopropyl phosphite butyl phosphite pentyl phosphite hexyl phosphite cyclohexyl phosphite heptyl phosphite nonyl phosphite decyl phosphite lauryl phosphite lorol phosphite cetyl phosphite octadecyl phosphite heptadecyl phosphite phenyl phosphite alpha or beta naphthyl phosphite alpha or beta naphthenyl phosphite benzyl phosphite tolyl phosphite mixed alkyl and aryl-substituted phosphites (either the mono-, di-, or tri-ester form) such as, for example:

methyl, phenyl phosphite dimethyl, phenyl phosphite amyl, phenyl phosphite diamyl, phenyl phosphite nonyl, phenyl phosphite (nonylphenyl) phosphite (4amylphenyl) phosphite 4-'amylphenyl, diethyl phosphite di-octadecyl, phenyl phosphite octadecyl, di-phenyl phosphite isobutyl, phenyl phosphite nonyl, tolyl phosphite nonyl, di-tolyl phosphite polyisobutenyl, diphenyl phosphite di-polyisobutenyl phosphite di-polyisobutenyl, phenyl phosphite (polyisobutenylphenyl) phosphite chlorethyl phosphite I chlorbutyl phosphite chloroctyl phosphite chlorphenyl phosphite chlorbenzyl phosphite 4 Y chlortolyl phosphite chlorpolyisobutenyl, diphenyl phosphite chlorpolyisobutenyl, ethyl phosphite polyisobutenyl (chlorbenzyl) phosphite polyisobutenyl (chlorpolyisobutenyl) phosphite Each of the above named specific compounds, if a monoor di-ester, may have its remaining valences of the trivalent phosphorus bonded to chlorine or bromine, where the phosphite ester is to serve as a reactant with an alkylene polyol.

The Lorol radicals mentioned above in connection with the specific phosphites that may be employed are derived from the corresponding primary alcohols obtained by the carboxylic reduction of cocoanut or palm kernel oils. These crude mixtures contain a major amount of lauryl alcohol together with minor amounts of octyl, decyl and myristyl alcohol. A typical Lorol alcohol mixture boils between about C. and about 190 C. at 50 mm. mercury pressure.

In addition to the conventional phosphite esters used as reactants, the present invention may likewise employ the condensates of aromatic compounds, preferably those having long chain alkyl groups attached thereto, reacted with the phosphorous trihalides such as phosphorous trichloride or phosphorous tribromide so as to effectuate compounds having the formula:

wherein R is a long chain alkyl-substituted aryl radical such as octylphenyl, octadecylphenyl, C alkylphenyl, C C alkylphenyl or similar compounds involving the substitution of naphthyl for phenyl and compounds involving the substitution of alkenyl for the alkyl groups. R and R may be the same as R or they may be the halogen component, i.e., an unreacted halogen moiety of the phosphorous trihalide, i.e., chlorine or bromine. A particularly useful material is wax-alkylated naphthalene reacted with phosphorous trichloride.

In order to effect the reaction of the aromatic hydrocarbons with phosphorous trihalide, a Friedel-Crafts type catalyst is employed, such as aluminum chloride, aluminum bromide, boron trifiuoride, using temperatures ranging between about 5 C. and about 100 C. for a period of time between about 1 andabout 20 hours. The reacted mixture is then contacted with sufficient water, or dilute acid to effectively destroy the Friedel-Crafts type catalyst and, at the same time, to hydrolyze the phosphite reaction product so as to remove all residual halide frbm the reaction product and to convert the same to the corresponding hydroxyl group if the phosphite ester is to be reacted with polyamine or amino alcohol; otherwise the hydrolysis is not necessary. Similarly, the aforementioned phosphite esters can also be treated with steam, water, or dilute aqueous mineral acid or alcohol such as ethanol or methanol in order to hydrolyze off the residual chlorine or bromine atoms present by reason of the trivalent phosphorous compound employed as the original reactant. The hydrolysis in connection with the phosphite ester treatment, is essentially only where the further reactants are polyamines or amino alcohols. It is generally carrried out at elevated atmospheric temperatures of the order of 50 to C. for from 1 hour to 3 hours. If necessary, sufficient superatmospheric pressure is maintained on the hydrolyzed mixture to insure that the phosphite material remains in the liquid phase.

After completion of the phospite esterification reaction or after completion of the Friedel-Crafts type reaction, in each case, followed by the partial hydrolysis treatment, if required, the reaction product is reacted with an amino aliphatic compound. These are of the class of alkylene polyamines and amino alcohols.

The alkylene polyamines are described in some detail 1n the Encyclopedia of Chemical Technology, Kirk Othmer, volume 7, pages 22-24 (1965), second edition. Representative examples of this class of compounds, any of which may be used, are the following:

ethylene diamine propylene diamine triethylene tetramine diethylene triamine decamethylene diamine tetraethylene pentamine tripropylene'tetramine pentaethylene hexamine di-(trimethylene) triamine tetra-(aminoethyl)methane tetramethylene diarnine.

Any of the amino alcohols may be used. The follow ing are representative examples of specific amino alcohols that may be employed:

2-amino ethanol B-amino propanol 2-arnino propanol di-(aminoethyl) diethylol methane 2-amino trimethylene glycol S-amino propylene glycol-1,2 4-amino-n-butanol 4-amino butanol-Z N-(Z-ethylol) ethylene diamine N-propylol diethylene triamine N-ethylol diethylene triamine N,N-propylol tetraethylene pentamine N,N-diethylol tetraethylene pentamine ethylene dinitrilo tetraethanol.

Representative examples of alkylene polyols which may be used are the following:

ethylene glycol propylene glycol-1,2 trimethylene glycol glycerol erythritol pentaerythritol tetramethylene glycol pentamethylene glycol hexamethylene glycol 2,2'-dihydroxy diethanol.

The reaction of the organic phosphites with the amino and/ or hydroxyl aliphatic hydrocarbons is carried out in liquid phase either in the presence or absence of inert solvents such as normally liquid hydrocarbon petroleum solvents, petroleum ether, hexane, cyclohexane, heptane, benzene, toluene, middle distillate, residual fuel oil, reduced crude oil, or lubricating oil fractions. The last named solvent is particularly desirable, for example, in cases where the final product is to be used in lubricating oils for the reacted mixture, upon purification, serves as a concentration containing anywhere from 50% to 75% of the active phospho condensate product as the active ingredient and constitutes a convenient method of market ing the novel compounds. The reaction is generally carried out at a temperature between about 0 C. and about 100 (3., preferably between about C. and about 50 C. The reaction time varies depending upon the reaction temperature employed but generally is between about 1 hour and about hours, preferably between about 3 hours and about 10 hours; after which the reaction mixture is allowed to cool to ambient temperature and if solvent has been used, and it is desired to remOve it, it is distilled off under atmospheric pressure or under vacuum if it is desired to do so. As previously pointed out, this is generally unnecessary if a middle distillate, residual fuel oil, reduced crude oil, or lubricating oil has been employed as the solvent.

The ratios and relative amounts of reactants vary considerably but, in general, between about 0.1 mole and 1.5

moles, preferably between about 0.5 mole and about 1 mole, of the alkylene polyamine, alkylene polyol, 01 amino alcohol are used per mole of phosphite hydroxy or haloester in cases where the said phosphite ester contains, for the most part, only one hydroxyl group or one halogen group per mole. While the required amounts of amino and/or hydroxyl-containing reactants are doubled if the phosphite ester contains two hydroxyl groups per mole of phosphite ester, in many instances, the organic phosphite ester will be a mixture of monoand di-hydroxyl-containing material but will predominate in one or the other depending upon the relative number of mols of alcohol or aryl hydrocarbon employed per mole of phosphorus trihalide employed in forming the original organic phosphite ester. In any event, it is desirable to employ a sufficient amount of the aliphatic amino and/or hydroxyl-containing compounds to completely react with all free hydroxyl or halogen groups contained in the organic phosphite ester; since this results in a compound having a higher molecular weight and possesses a greater degree of oil solubility in the final phospho additive.

Many of the phosphites above mentioned are available commercially. For those specifically enumerated above which are not available commercially, it is a simple matter to effect a reaction between phosphorous trichloride or tribromide and the corresponding monohydric alcohol in which the molar ratios of the alcohol to the phosphorous compound are maintained between 1:1 and about 3:1 depending upon whether or not it is desired to produce a mixture predominating in the mono-, di-, or triphosphite ester. Preferably a mole ratio of alcohol to phosphorous trihalide of between about 0.75 :1 and about 3.5 :l is maintained. Any solvents which are employed in elfectuating the reaction are distilled off at atmospheric pressures or under slight vacuum, unless concentrates of active phospho ingredient in a middle distillate, residual fuel oil, reduced crude oil, or lubricating oil fractions are tobe produced.

The novel phospho products are useful in lubricating oil compositions of the type customarily employed in internal combustion engines of either the gasoline or diesel type as well as for the lubrication of heavy duty gas engines. The amounts incorporated into such lubricating oils range between about 0.01 and about 10.0 wt. percent generally, preferably between about 0.01 and about 5.0 wt. percent. Additionally, the novel additives herein described are useful in middle distillate fuels, residual fuel oils, and reduced crude oils for the purpose of imparting antirust, anticorrosive, and fiowability properties to such materials into which the additives are incorporated including gasoline, jet fuel, kerosene, heating oil, heavy residual fuel oil such as Bunker-C, and reduced crude oils. When so used, the additives are incorporated in amounts ranging between about 0.01 and about 5 .0 wt. percent, preferably between about 0.01 and about 1.5 wt. percent. All of these percentages are based on the total weight of the composition.

The fuels and lubricating oil compositions described may also include other conventional additives present in like or smaller amounts. For example, they may contain oxidation inhibitors such as phenyl alpha naphthylamine; rust inhibitors such as the over-based alkaline earth metal petroleum sulfonates; detergent additives such as overbased calcium petroleum sulfonate, zinc dialkyl dithiophosphates, phosphosulfurized polyisobutylene, barium phenate sulfide, phenol sulfonates; viscosity index improvers such as the polymers and copolymers of long chain alkyl acrylates and methacrylates, the polymers and copolymers of long chain alkyl .fumarates, polyisobutylene, the aryl and alkyl phosphates; the pour point depressants such as wax-alkylated naphthalenes, and the like. In addition, they may contain other ashless dispersants such as polyisobutylene-substituted succinic anhydride condensation reaction products with polyethylene polyamine such as tetraethylene pentamine.

A typical lubricating oil fraction of the SAE 10-W-30 grade is representative of automotive lubricating oils conventionally available. This was employed in carrying out certain of the tests described in the examples. The base oil was composed of about 90% of a solvent-extracted, dewaxed, neutral oil from Mid-Continent paraflinic crude. It had a viscosity of 105-115 SUS (Saybolt Universal Seconds) at 100 F. and a pour point of about F. The remaining 10% of the base oil blend was the same type of oil but had a. viscosity of about 450-500 SUS at 100 F. The oil also contained, in all tests, approximately 10% of a viscosity index improver, namely, polyisobutylene and about 3.75% of an ashless dispersant identified as the polyisobutenyl succinic anhydride imide of tetraethylene pentamine. Minor amounts, i.e., less than 1%, of overbased calcium petroleum sulfonate and wax-alkylated naphthalene were also present. The amount of novel additive employed in the base oil for test purposes was, in all cases, 1 wt. percent based upon the total weight of the composition.

Two types of tests were carried out to test the efiicacy of the herein described novel additives. In one test known as the Falex wear test, a Falex wear test machine was operated with the test oils for 30 minutes under 500 lbs. per square inch direct pressure gauge reading on a bearing having a rotating steel pin and then determining, at the end of this time, the milligrams of wear on the steel pin used in the test. The test was conducted for the purpose of measuring the amount of wear which the bearings would encounter under extremely severe conditions and while using the test oil compositions.

Another test was carried out known as the cyclic temperature sludge test which evaluated the sludge-handling ability of the tested lubricating oil compositions. In this test the temperature of the oil was cyclically raised and lowered over a period of stated hours in order to determine the oxidation stability and the sludge inhibiting or sludge forming tendencies of the novel additives in the oil compositions. A 6-cylinder Ford engine was used which employed a standard carburetor. It was operated at a standard speed of 1,500 rpm. :15 r.p.m. under a constant load of 1401-2 foot lbs. of torque. The oil sump temperature was maintained in the cold phase at 150 F. 1 :5 F. and in the hot phase at 215 F. :5" F. The cold phase operation was for a period of 5 hours and alternated with a hot phase operation of 2 hours.

Still another test was carried out (see Example 7) known as a lubricant stability test which evaluates the compounded oils under accelerated oxidative conditions. The method is designed primarily to evaluate the stability of railroad diesel lubricants wherein the compounded oils are subjected to elevated temperatures (342 F.) for a period of 23 hours in contact with copper-lead alloy, and silver, bearing metals, i.e., those encountered in heavy duty diesel engines. Air is bubbled through the test oil while stirring it under these conditions and for the length of time indicated. Air is bubbled in at about 2 cubic feet per hour and the stirrer is rotated at about 600 r.p.m. Fresh metal specimens are inserted into the oil every three hours. Saybolt viscosities at 100 F. are measured and the rating of the oil is computed on the basis of percent viscosity increase after 23 hours.

The invention will be more completely understood by reference to the following examples but it is not intended that the invention be limited to these examples since they are only representative and exemplary in nature. All percentages are in terms of weight percent of the total composition.

EXAMPLE 1 600 grams of nonylphenol were gradually added to 414 grams of phosphorous trichloride at a temperature of 10 C. over a period of 2 hours. The mixture was stirred at room temperature thereafter until there was no further evolution of gas. 70 grams of this material was then adde over a period of 0.5 hour while maintaining the temperature at about C. to about 20 grams of ethylene glycol. Thereafter the reacting mixture was heated to that temperature for an additional 8 hours. The product had a phosphorus content of about 8.75%.

EXAMPLE 2 About 200 grams of the nonylphenyl phosphite ester, as prepared in Example 1, was hydrolyzed by mixing about 20 cc. of water therewith at a temperature of about 10 C. Thereafter the excess water was distilled from the hydrolyzed mixture at a temperature of 40 C. while under a vacuum of 1 mm. of mercury. About grams of this hydrolyzed product was added to about 10 grams of diethylene triamine over a period of about 30 minutes while maintaining a temperature of about 100 C. The resultant mixture was thereafter heated at this same temperature for an additional 8 hours. The product had a nitrogen content of 3.7%.

EXAMPLE 3 About 200 grams of Lorol alcohol were gradually added to about 137 grams of phosphorous trichloride while maintaining a temperature of about 10 C. After all evolution of gas had ceased, about 68 grams of pentaerythritol were added in small increments and the reaction was thereafter maintained at about 25 C. for a period of about 20 hours with stirring. The product had a phosphorus content of about 4.22%.

EXAMPLE 4 About 500 grams of parafiin wax alkylated naphthalene as a 50% concentration in a lubricating oil (derived from solvent-dewaxed, neutral Mid-Continent crude) having a viscosity of about SUS at 100 F. was admixed with about 20 grams of aluminum chloride and about 40 grams of phosphorous trichloride with stirring at about 60 C. for about 6 hours while maintaining a nitrogen atmosphere in the reaction zone. The reacted mixture was then hydrolyzed with about 100 cc. of water and the excess water was removed, the product was water washed with an additional 100 cc. of water and the water completely removed from the product by using a separatory funnel. The product had a phosphorus content of about 0.24 wt. percent based on the total recovered reaction mixture. About 200 grams of this phospho-derivative including the lubricating oil solvent was heated with about 8.4 grams of tetraethylene pentamine at about 150 C. for about 8 hours. The resultant phospho product had a nitrogen content of about 0.83% based on the total recovered reacted mixture which included the oil solvent.

EXAMPLE 5 Each of the products of the foregoing examples was tested in the previously described SAE 10-W-30 oil blend as a base oil. The test in each instance was the cyclic temperature sludge test, was carried out as hereinbefore described, and with the following recorded data being obtained.

TABLE.OYOLIC TEMPERATURE SLUDGE TESTS NorE.A1i additions except test E were in concentration of 1.0 wt. active ingredient.

I Iating of 10 indicates no sludge. Rating of 0 indicates worst possible s u gmg.

1 Oil E contained 3.8% of Example 4 (70% active ingredient) but did not contain the before mentioned succiuie anhydride imide sludge dispersant.

From the above table it is apparent that oil blends of the novel phosphorus containing compound are far superior to the base oil. Each 21-hour period of engine test is approximately equivalent to 1,500 miles stop-and-go type driving. Therefore, this is considered to be a significant improvement.

EXAMPLE 6 The compound, in oil concentrate form, produced in accordance with Example 4 was further subjected to the Falex anti-wear test but, in this instance, 3.78% of the additive (70% active ingredient) was employed. In this case, however, the base oil did not contain the ashless dispersant polyisobutenyl, succinic acid imide, of tetraethylene pentamine.

The base oil did contain a small amount of the zinc salt of the di-(C -C alkyl) dithiophosphate. The weight loss of the tested oil containing the base oil alone was 9.4 milligrams. The base oil containing the tested additive showed a wear of about 2.6 milligrams. It is, of course, readily apparent that the novel additive greatly enhanced the antiwear properties of the oil.

EXAMPLE 7.-LUBE STABILITY TEST Percent viscosity increase after 23 hours Base oil 100 Base oil +1% sample of Example 1 4.3 Base oil +1% sample of Example 2 2 Both of the additives from Example 1 and Example 2 showed excellent oxidation resistant properties when compared to the base oil.

Having now thus fully described and illustrated the nature of the invention, what is desired to be secured by Letters Patent is:

1. A hydrocarbon composition comprising a major amount of a liquid hydrocarbon selected from the group consisting of lubricating oils, middle distillate fuels, re-

sidual fuels and reduced crude oil and between about 0.001 and about 10.0 wt. percent of the reaction product of an organic phosphite ester having the formula:

wherein R is a radical selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl, alkenyl, alkaryl and the chloro derivatives thereof, R and R being selected from the group consisting of the same group as R and hydrogen, at least one of R and R being hydrogen, and a compound selected from the group consisting of alkylene polyamines and amino alcohols.

2. A hydrocarbon composition comprising a major r amount of a liquid hydrocarbon selected from the group consisting of lubricating oils, middle distillate fuels, residual fuels and reduced crude oil and between about 0.001 and about 10.0 ft. percent of the reaction product as in claim 1 wherein the phosphite is a hydroxy mono or diester and the other reactant is an alkylene polyamine.

3. A hydrocarbon composition comprising a major amount of a liquid hydrocarbon selected from the group consisting of lubricating oils, middle distillate fuels, residual fuels and reduced crude oil and between about 0.001 and about 10.0 Wt. percent of the reaction product as in claim 1 wherein the phosphite is a hydroxy mono or diester and the other reactant is an amino alcohol.

4. A hydrocarbon composition comprising a major amount of a liquid hydrocarbon selected from the group consisting of lubricating oils, middle distillate fuels, residual fuels and reduced crude oil and between about 0.001 and about 10.0 wt. percent of the reaction product (ill 10 as in claim 2 wherein the phosphite is a monoester having the formula:

wherein R is selected from the group consisting of alkyl, chloralkyl, aryl, chloraryl, aralkyl, chloraralkyl, cycloalkyl, chlorcycloalkyl, alkenyl, chloralkenyl, alkaryl and chloralkaryl.

5. A hydrocarbon composition comprising a major amount of a liquid hydrocarbon selected from the group consisting of lubricating oils, middle distillate fuels, residual fuels and reduced crude oil and between about 0.001 and about 10.0 wt. percent of the reaction product as in claim 3 wherein the phosphite ester is a monoester and has the formula:

RO-P

wherein R is selected from the group consisting of alkyl, chloralkyl, aryl, chloraryl, aralkyl, chloraralkyl, cycloalkyl, chlorcycloalkyl, alkenyl, chloralkenyl, alkaryl and chloralkaryl.

6. A hydrocarbon composition comprising a major amount of a liquid hydrocarbon selected from the group consisting of lubricating oils, middle distillate fuels, re-

sidual fuels and reduced crude oil and between about 0.001 and about 10.0 wt. percent of the reaction product as in claim 2 wherein the phosphite is nonylphenyl phosphite dihydroxy mono-ester and the polyamine is diethylene triamine.

7. A hydrocarbon concentrate of a liquid hydrocarbon selected from the group consisting of lubricating oils, middle distillate fuels, residual fuels, and reduced crude oil containing between about and about wt. percent of the reaction product of an organic phosphite ester having the formula:

R o-P wherein R is a radical selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl, alkenyl, alkaryl and the chloro derivatives thereof, R and R being selected from the group consisting of the same group as R and hydrogen, at least one of R and R being hydrogen, and a compound selected from the group consisting of alkylene polyamines and amino alcohols.

References Cited UNITED STATES PATENTS 2,151,300 3/1939 Moran et al 25249.9 2,847,442 8/1958 Sallmann 260'--985 X 3,170,902 2/1965 Nagelschmidt et a1. 260-985 X 3,180,832 4/1965 Furey 25256 3,309,431 3/1967 Mark 252400 3,318,811 5/1967 Conradi et al 25249.9

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