US2252675A - Stabilized hydrocarbon composition and stabilizing agent therefor - Google Patents

Description

Patented Aug. 12, 1941 STABILIZED HYDROCARBON CODHOSITION AND STABILIZING AGENT THEREFOR Carl F. Prutton, Cleveland Heights, Albert K. Smith, Shaker Heights, and Delton R. Frey, East Cleveland, Ohio, assignors to The Lubri- Zol Corporation, Wic

of Ohio klifle, Ohio, a corporation No Drawing. Application March 6, 1939,

Serial N0. 260,220

24 Claims. (01. 252-53) This invention relates, as indicated, to the stabilization of hydrocarbon compositions. The term hydrocarbon compositions as used-herein, is intended to include liquid compositions which are essentially derivatives of petroleum, naturally occurring oils of the type represented by animal, vegetable and marine oils and derivatives of the same.

More specifically, this invention relates to the stabilization of hydrocarbon compositions, such as lubricants which are usually essentially mineral oil. This invention also is applicable to the stabilization of lighter fractions of petroleum such as are used as fuels. 7

Certain subject matter disclosed but not claimed herein is disclosed and claimed in copending applications Serial No. 260,221, filed March 6, 1939, and Serial No. 395,234, filed-May 26, 1941.

It is well known that liquid hydrocarbon compositions of the character above identified are subject to deterioration as by oxidation and polymerization, for example but not by way of limitation, during storage and handling and are also subject to deterioration which proceeds at a more rapid rate during use of these compositions.

For example, the various oils mentioned above 7 and the lighter fractionsused as fuels have a tendency on storage to oxidize, polymerize, or otherwise deteriorate to form gums and thelikej and when such compositions are used, particularly under conditions of high temperature, de-

terioration proceeds at a more rapid rate to the production of gums, sludges and other oxidation and/or polymerization-products. This deterioration is manifested by discoloration of the liquid hydrocarbon body; the generation within the body of flocculent material; the precipitation from the body of the more serious types of deterioration products; such as sludge, and the deposit of var tend to cause deterioration of such oil composition. Oxidation and/ or sludgingof liquid hydrocarbon compositions employed as lubricants in suchengines'is usually accelerated by the rela-.

tively high temperatures to which such compositions are subjected. This is particularly true in engines of the Diesel type in which the opject to thevarious conditions above named which crating temperatures are generally somewhat higher than those in the so-called ignition type.

It is a principal object of our invention, therefore, to provide for the stabilization of compositions of the character defined in order to reduce the tendency of the same to decompose particu .larly in the manner indicated.

It will also be observed that the addition agents employed for the prescribed purpose are in themselves new compositions of matter.

such compositions under conditions of use, by the inclusion therein of a minor proportion of the product resulting from the reaction of a hydroxy ester or an organic hydroxy-acid with a reagent which comprises phosphorus in tri-valent form and a halogen. It also comprises the similar use of certain derivatives of these reaction products.

As hereinafter more fully explained, the stabilization of certain types of liquid hydrocarbon compositions and especially when the same are used for certain specific purposes, may be effected by the inclusion therein of certain derivatives of the aforesaid reaction product or products or portions thereof, which derivatives may be prepared, for example, by halogenation and/or treatment with an alkali or other base to form a salt, or ester-salt.

As previously stated, our invention contem plates the use, as stabilizing agents, of the products resulting from a. specified reaction. We therefore list below specific examples of the two classes of reactants which may be employed in the preparation of the product which we employ as the stabilizing addition agent.

The phosphorus and halogen containing reactants As indicated above, any material which contains phosphorus in tri-valent form and a halogen, which material will react with a hydroxy ester, may be employed in the preparation of an addition agent. Of these phosphorus andhalogen containing reactants, PC13 will be found .to

be particularly useful and productive of suitable I addition agents. Other reactants of this class are as follows:

Phosphorus tri-bromide, PBra. Phosphorus tri-iodide, PIa

Phosphorous oxy-chloride, POCl Phosphorous sulpho-chloride,PSCl

the

Halogen derivatives of phosphin'e and organic substituted phosphines. e. g.

Phosphenyl chloride, (CsHs) PCi: Compounds of the classes:

(a) RPCI: and RR'PCl, and (b) ROPCI: and (R) (R'0)PC1 in which R and R are organic radicles such as:

Aromatic. e. g.

Phenyl' v Cyclohexyl phenyl Alkylated phenyi Aliphatic, e. g. Lauryl Cetyl. y Cycloaliphatic, e., g. Cyclopentyl Cyclohexyl The hydrozw esters The esters which are suitable for use as one of the components of the reaction with'phosphorus and halogen containing reactants in the preparation of the stabilizing addition agent of our invention may, for example, be any of the esters produced by reacting any of the alcohols,

' and preferably any of the monoor di-hydroxy low molecular ,weight alcohols, such as any of the following:

- Methyl alcohol Ethyl alcohol Propyl alcohol Butyl alcohol Ethylene glycol Propylene glycol Trimethylene glycol Cyclohexanol Benzyl'alcohol Furfuryl alcohol (1) Monobasic acids:

(a) Monohydroxy: e. g.' Glycollle acid Lactic acid Hydracrylic acid Hydroxylbutyric acids 1 (b), Polyhydroxy: e. g.

Glyceric acid- Dihydroxypalmitic acid (2) Polybasic acid (a) Monohydroxy: e. g.

"Tartronic acid Malic acid Citramalic acid Citric acid b) Polyhydroxy: e. g.

Tartaric t V t Trihydroxy glutaric acid 7 In general, the esters of the low molecular weight hydroxy-fatty acids are preferred.

We have found the methyl esters to be prefer able for our purpose in most cases; I

The following-are illustrative of specific embodiments of our invention: a A material, which for purposes of convenience in referring to the same herein we shall desighate as RM. L., is prepared bythe reaction of methyl lactate with PCla. The relative propor tions 'of. methyl lactate and PCI: used in :the preparation of P. M. L. are given in the-following Example I (P, M. L.)

Methyl lactate 104 parts by weight PCla 45 parts by weight Weight of product 74.5

Weight of material removed by distillation 31.8. Yield; 65% Average mol. wt 312 Boiling point 230 C. 10 Melting point Liquid at r 0 cm g I temperature Sp. gr. at C -.1.252 Ref. index at 26 CL. 1.4365 Color Light yellow 15 Phosphorus 10.9% Chlorine 1.12% Acid No 415 Soluble to extent of about 1% in Penna 150 (S. U. S. at 100 F.) neutral. Completely miscible with .water and ethyl alcohol.

The methyl lactate is placed .in a reaction vessel equipped with an agitator and reflux condenser. The vessel and agitator are preferably of glass or enamel. The PO13 is added slowly and l the temperature begins to decrease, indicating that the PCI: has reacted to some extent with the methyl lactate. The slow addition of PC13 accompanied by stirring until a decrease in temperature is noted insures against loss of PC]: whose boiling point is 76 C. andalso gives a higher yield than when these precautions are not taken. After the temperature of the react ants has begun to drop, heat is applied and the temperature of the reactants is raised to 120 C. This temperature is maintained for 3-hours. A slight reaction is apparent until the mixture has :been heated at 120 C. for about 2 hours and minutes. The mixture is stirred continuously all 'for liquid hydrocarbon compositions'or the end product may be distilled at atmospheric pressure and all of the material which distills over at 130 table, aswell as the properties of the end product. 7

C. or less may be discarded. Whether the end product as producedfor the refined end product derived by removal of the more volatile products is used, depends largely upon the use for which the ultimate composition containing the stabi lizing addition agent is designed. In general, the less volatile part of the reaction product, or

that part which contains combined phosphorus,

is preferred for our purpose.

We believe the reaction produces two general types of compounds: u

. (a) Chlorine-containing compounds, for example the type in which chlorine has been substituted for the hydroxyl group of the hydroxy- .ester; and

(b) Phosphorus-containing compounds, for

example the type in which the ,hydroxyl group has lost hydrogen (which forms HCl with chic rine removed from the P011100 that the omen (the rei'ined material) to several diflerent repot the hydroxyl group becomes attached to a resentatlve commercial oils, and oils treated with phosphorus atom. other addition agents.

Composition Oxidationtcat Conradson I Cormm z ia Hen- "mm Viscosity 8.18.3210 Naphtha Insoluble g: 5. g? 3? Methyl 110m Percent (leadstearste stearste P.M.L. Percent bronze) phenyl benzene a a 48 W Hours ML 6 I oxide Original hm Orlzlnsl hour. 7 up for i0r100 hum a mg. 111:.

treated 4 2 .00 .00 .00 541 00.4 10.4 14.0 0 00 -.20

' um-con'rmm'r 0.4. 11.00 010 '10s on.

treated I 1 4-- .00 .40 1.11 00.0 00.0 1.1 01.0 0 42 -.02 0 .00 .40 1.01 01.1 11.0 50 .200 0 00 0 .00 .00 .00 1.02 000 10.1 100 11.0 45 111 -.01 1 .00 .00 .00 .01 1.20 001 000 0.2 01.0 0 04 --12 0 .00 00 .20 .41 200 010 122 11.2 15.0 40 110 02 0 .50 00 20 .25 00 .10 1.10 02.1 00.0 11.1 00.0 .5 40 00 00051510100101. 0. .4 10. 10 0101011 OIL nsvmc A v. 1. or 01 treated 11 .00 .04 100 42.1 .405 00 105 41.0 100 01 12..-... .00 .00 .00 0.12 420 400 14.0 0.0 20.0 414 10. .00 .00 .00 .01 1.54 420 450 1 0 10.0 40.0 100 00 PENNSYLVANIA 0. A. 10. 40 MOTOR OIL e treated 15-.- .00 1.40 251 00.0 051 15s 4 0 2- 40 10.-- .00 1.01 201 00.0 000 104 4 0 2 as 11 .00 .00 151 0.04 02.0 1040 20.5 4 5 0 -.00 10 .00 .00 .00 1.24 202 01.4 04.0 150 4 4 0.1 -.o0 10-.- .00 .50 .25 1.10 2.00 10.0 00 0 042 4 0 e 05 20....- .00 .50 20 .20 .00 1.40 2.00 01.0 04.0 10.0 4 0 0.0 10

rsrmsrnvmrs s A 11 10 MOTOR om .00 .10 .40 40.5 41.0 2.0 4(040 0 2 -.04 .00 .00 .50 400 41.0 20 4 0 a -.01 .00 .10. 1.40. 450 000 01 210 5 00 -1.40- .00 p .00 .20 .15 400 401 0.0 00.5 0 11 -.00 .50 20 .25 .21 1.10 405 000 1.0 20.0 0 00 -1.40 00 20 .25 .00 -01 .01 41.2 40.1 a 0 00.0 0 10 11 .15 .10 1.10 41.0 000 1.4 200 0 45 -1. 15 .15 .00 .10 .01 400 40.0 5.1 04.0 Y 0 00 -.01

1545mm. e-did not produce 10 11min 48 hours.

b-did not produoeiil) 111s. hours.

lbr example in the reaction oi lactate The determinations which appear in the forewith P311, part a would be principally the methyl soins table. such as, tor-example. Qonradson'carester ot-chlor propionic acid and part b prinhon. viscosity determinations, and naphtha in-.

cipally esters of phosphdrous acid I such as soluble. ,were determined on samples prepared P(OC1H4COOCH0)0 and .RQHwCflflCOOQBfly w by an caidation test procedure which is, in every It appears thatthe constltlients o! the reaction respect, similat to that prescribed by the Stand- 0100001 described 44 41-401 444 responsible or aid 01 1001 4 oxidation test, excepting 01141 4 the stabilising elect when the product is wed piece 0! ironfiire is submerged in the oil during in accordance with our invention. 110 0100101- the test. 5'1 I most purposes, part a is not deleterious. and tor 45 The data given in the column headed "Corrosome purposes may even be advanta seoilly insion has 044 determined in accordance with,

eluded. Part sis in 441150010000000140410 than the standa'rdlflhell corrosion test using lead art b and may therefore-be easily separated bronzeasthemctal.

from the latter, by distillation at atmospheric or A series or tests substantially duplicating those subatmospheric pressure. 1 liven 10104051440104 table but 011151 07 1 8 the The specific pmperties iven in the table capunretlned P. M. 11., i. e.. the product immediately tioned "Example No. I" are those for the reilned resultins from .the reaction between methyl lacmaterial. tate and P010. nd vlthoutdistillinsefl anyot The tollowinz table gives the results obtained the end product as hereinbeiore specified. were by the additionoiminoraasoudsotPJLI-JI runwithsubstantialiythesameresuitsasthcae given in the foregoing table. It would appear, therefore, that it is not necessary for most uses to refine the P. M. L. before it is used as an addition agent.

i; Another product which we shall hereinafter, for convenience, refer to as P. B. T. was made by reacting dibutyl tartrate with PCI; under substantially the conditions previously specified for the manufacture of P. M. L., and the following is a table giving the proportions by weight of the reactants used and the properties of the end product.

Example II (P. B. T.)

Dibutyl 65 parts by weight PCla 11.6 parts by weight Weight of product". 60 Weight of refinedmaterial.55.5 Yield 90% Boiling point 235 C.245 C.

Melting point Liquid atroomtemperature Tests on oils similar to those given above in connection with the study of the properties of P. M. L. were run using P. B. T., and the latter was found to be substantially as efiective as P. M. L. v

Another material which we shall hereinafter, for convenience, refer to as P. M. C., was made by the reaction of trimethyl citrate with PCla. The proportions of reactants used and' the properties of the end product-are given inthe following table: I

' Example III (P. M. c'.)

Trimethyl citrate 500 parts by weight PCl: 75 parts by weight Weight of product 480 I Weight of refined materiaL- 465 Yield 92% Melting point '80-100 C.-

Tests on this material in oil to determine its eflect similar to those tests previously given in connection with the study of the eifect of P. M. L. were run and show that P. M. C. was similar to P. M. L., i e, eflective to retard deterioration of the oils. P. M. C. has a tendency to be corrosive with respect at least to certain of the more sensitive metals, and, therefore, when such metals are encountered it would be advisable to employ minor amounts of corrosion inhibitors, such as the alkyl anriaryl phosphites, along with the P. M. C. I

Our invention also contemplates the employmentas a stabilizing agent of the reaction proda ucts which may be prepared by eitta' of the following methods, viz:

(a) Reacting a reagent, which comprises phosphorus in tri-valent form and halogen, with a mixture of hydroxy esters. a mixture of organic hydroxy acids or a. mixture of one or more hydroxy esters with one or more organic 'hydroxy acids.

(b) Reacting a reagent, which comprises phosphorus in tri-valent form andhalog en, with one or two molecules of a hydroxy ester oranorganic hydroxy acid per molecule. ofreagent and then completing the reaction with another re ctant oi. the class. consisting of hydroxy este s and organic hydroxy acids diflerent from that which was initially employed.

v is stabilized the addition agents commonly em-- A lines such as The reaction products thus prepared are especially desirable for use for certain purposes on account of their complexity.

Very small amounts of our addition agents above identified, are effective, in most. cases less than one percent, and usually a fraction of 1%, e. g. from about 0.001 to about 0.2% will be found most useful. For use in mineral lubricating oil (e. g. a motor oil for automobile, aviation, or Diesel engines) amounts from about 0.01% to about 0.1% are suitable, and usually the reaction product with an alkali (e. g. sodium,

potassium, ammonium, or substituted ammonium, hydroxides) in aqueous solution. Ester-salts may be formed by the partial saponiflcation of esters of polybasic acids, 'e. g. the phosphoruscontaining reaction product of P01: with dibutyltartrate may be partly saponlfled with caustic soda to form the corresponding butyl-sodium ester-salt. Similar salts and ester salts of metals other than the alkali metals may be formed directly by reacting the ester with the metallic base, or more readily by double-decomposition of the alkali salt (or ester-salt) with a salt of the othermetal. I

As above indicated, our addition agents are suitable for the purpose of stabilizing liquid hydrocarbons generally, among which may be mentioned refined mineral oils of the character generally employedas lubricants, lighter fractions andcuts such as are employed as fuels in Diesel type engines and even lighter fractions and cuts which are commonly identified as gasoline. Other oils such as hydrogenated oils and voltolized I oils may be similarly stabilized by the inclusion therein of the above-mentioned addition agents.

The liquid hydrocarbon compositions which may be stabilized by the use of the addition agents hereinbefore specified need not be pure hydrocarbons but may contain other addition agents such as extreme pressure addition agents on the order of halogen, phosphorus and/or sulfur compounds, as well as corrosion inhibitors,

such as phosphorus compounds, etc. and other additions commonly, employed, such as pourpoint depressors and the like.

When a lighter fraction, as above indicated,

ployed in" such lighter fractions may also be present; as for example,-"the variou s dopes" commonly employed in Diesel fuels, and antiknock compounds commonly employed in gasotetra-ethyl lead, iron carbonyl, etc.

In general, the addition agents of this invention will-not be found incompatible with com 'monly employed antioxidants such as are used in gasolines' and the like.

There may, however, be certain of these other addition agents which might be found incompatible with the addition agents of the present invention and in such cases, of course, the in-- compatible addition agent, whatever it may be, should be omitted, since it will usually be found that a compatible addition agent for the desired purpose will be available among others of those available.

Among the other addition agents with which the compounds of the present invention may be employed to advantage, as above stated, are the extreme pressure addition agents, such as the halogen, phosphorus and/or sulfur-containing compounds. n

In general we have found that the addition agents of the present invention do not detri mentally affect the extreme pressure characteristics of a mineral lubricating oil, for example,

as other advantages flowing from the combination of the constituents named. For example, it

is within the contemplation of our invention to add to a light hydrocarbon fraction such as gasoline or Diesel fuel, minor amounts of a heavier which characteristics are the result of the presence therein of the extreme pressure addition agents above named. Moreover, where the addition agents of the present invention have been tested in lubricating compositions which also contain certain other addition agents, the extreme pressure characteristics of the resultant composition has been somewhat improved and such improvement has been traceable to the presence therein of the compounds of the present invention.

Throughout the foregoing specification and in the appended claims, reference is made to "oil-' soluble and by such term, as used herein, it is liquid hydrocarbon such as refined mineral lubricating oil to which has been added a minor amount of the addition agents which characterize the present invention. Such combination, 1. e., a? major proportion of gasoline to which has been added a minor amountof a mineral oil of lubriintended to indicate the ability of the addition agent to form not only true solutions with the oil to which the same are added, but also the ability to form therewith any form of substantially permanently homogeneous composition.

With certain of the more difflcultly soluble addition agents to which this application relates,

it may be advantageous to employ a mutual solvent as one means for increasing the "oil-solubility of the addition agents and to also incur-- porate the addition agents in the 011 base by special homogenizing apparatus, such as for example, that described in' Cornell Patent No.

oil-soluble" to any extent and which may not be incorporated in such a way as to effect any improvement in the oil, will obviously be excluded by the term oil-soluble, as employed in the specification and in the claims.

In general, the addition agents prepared in the manner specified will be sufllciently nonvolatile so as to find usefulness for the purposes specified.

from the liquid hydrocarbon and those which will not be decomposed by the temperatures which- In cases, however, where high temperatures are encountered, it will be best to select those which will neither substantially evaporate 1 compounded heavier hydrocarbon added to the lighter hydrocarbon fuel for optimum results will be found 'to be in the vicinity of 30%, i. e., in the range of from about 0.15% to 0.60%.

It will be observed that the addition agents mentioned above may be generally classified as follows:

(1) nhr-oa'ooom OR'COORI (2) (OHM V oa oooiy and o-n'coom (a P-o-Iucoo1z I o-rucoori where R, R- and R, are organic radicles; and R, R -and R. are organic radicles, hydrogen, a metal, or a metallic radicle.

R! 1 \P0R'CO0R' 0-R'CO0RI (2 re 1 I o-a ooon where R", R, R and ,R' are organic radicles and R. and R. are organic radicles, hydrogen, a

cating viscosity for lntema'l combustion engine 'use, along with aminor amount of the addition agents which characterize the present invention, produces a fuel for internalcombustion' engines which is particularly desirable for ,use on account of the nature of the deposits left by the fuel in the combustion chamber, as well as the general performance of the fuel.

For proper results, when the compounded relatively-heavier liquid hydrocarbon is essentially mineral oil having a' viscosity of from about'50 to about 250 seconds Saybolt Universal at R, such composition should be added to the usually lighter hydrocarbon fuel of the type boiling within the gasoline range in quantities varying from .05% to 1.50% by volume. The amount of metal, or a metallic radicle.

which form.

which-the phosphorus is trivalent.

where R, R R and R are organic radicles and R and R are organic radicles, hydrogen, a metal, or a metallic radicle. I

- Other modes of applying the principle of our invention may be employed insteadof the one explained, change being made as regards the materials employed, provided the ingredients stated by any of the following claims or the equivalent of such stat ployed. v

We, therefore, particularly point out and distinctly claim as our invention:

1. A lubricating composition comprising a major proportion of mineral oil, the properties of which afiecting its use as a lubricant are improved by the inclusion therein of a minor-proportion of an oil-soluble product resulting from ed ingredients be emvalent state, at least one bond of which is attached to the radicle ORCO0R where R is an organic radicle and R is selected from the class consisting of an organic radicle, hydrogen, a metal and a metallic radicle.

"I. A lubricating composition comprising a major proportion of mineral oil, the properties of which affecting its use as a lubricant in the crankcase of an internal combustion engine are improved by'the inclusion therein of a minor proportion of the phosphorus-containing product resulting from the reaction of an ester of a mono-basic hydroxy acid with a phosphorus and halogen-containing compound of the type in which the phosphorus is present in tri-valent form.

8. A lubricating composition comprising a major proportion of mineral oil, the properties of which affecting its use as a lubricant in the crankcas of an internal combustion engine are improved by the inclusion therein of a minor proportion of the phosphorus-containing product resulting from the reaction of an ester of a saturated mono-basic hydroxy acid with a phosphorus and halogen-containing compound of the type in which the phosphorus is present in tri-valent form.

9. A lubricating composition comprising a major proportion of mineral oil, the properties the reaction hydroxy-ester With a 1 of which aifecting its use as a lubricant in the major proportion of mineral oil, the properties of which afiecting its use as a lubricant in the crank-case of an internal combustion engine are improved by .the inclusion therein of a minor proportion of the phosphorus-containing product resulting from the reaction of an ester of an organic hydroxy-acid with a. phosphorus and halogen containing compound of the type in the phosphorus is present in tri-valent 3. A lubricating composition comprising a crankcase of an internal combustion engine are improved by the inclusion therein of a minor proportion of the phosphorus-containing product resulting from the reaction of an ester of a low molecular weight saturated mono-basic hydroxy acid with a phosphorus and halogen-containing compound of the type in which the phosphorus is present in tri-valentform.

10. A lubricating composition comprising a major proportion of mineral oil, the properties of which affecting itsuse as a lubricant in the crankcaseof an internal combustion engine are improvedby the inclusion therein of a minor proportion of the phosphorus-containing product resulting from the reaction of an ester of a major proportion of mineral oil, the properties of which aflecting its use as alubricant in the crankq'case of an internal combustion engine are improved by the inclusion therein of a minor pro- Iportionof' the phosphorus-containing product low molecular weight saturated mono-basic hydroxy acid and a mono or di-hydric alcohol with a phosphorus and halogen-containing compound of the type in which the phosphorus is present improved by the inclusion therein of a minor crankecase ot aninternal combustion engine are improved by the inclusion therein of a minor proportion of the phosphorus-containing product relsulting from the reaction of PC13 with trimethyl citrate. I

@5. A lubricating composition comprising a major proportion of lubricating oil, the resistance ,of which to the formation of deleterious products when exposed to high temperatures under condi- 'tions of use is improved by the inclusioriitherein ot a minor'proportionof an oilesoluble, phosphorus-bearing derivative of an organic hydroxy-acid which derivative is obtained irom the reaction product oi th acid with a phosphorus-- and halogen-containing reagent of the type in 6. A composition oi? matter comprising -a major proportion of a liquid hydrocarbon having included in solution therein a minor'proportion oi' a compound containing phosphorus in -triproportion of the phosphorus-containing product resulting from the reaction of an ester of a low molecular weight saturated -mono-b asic hydroxy acidand a low molecular weight mono ordi-hydric alcohol with a phosphorus and halogen-Icontaining. compound of the type in which the phosphorus is present in tri-valent form.

12. A lubricating composition comprising a improved by the inclusion therein '0! a minor- I proportion of the phosphorus-containing product resulting from the reaction of an ester of, a low molecular weight saturated mono-basic hydroxy acid and a low molecular weight mono-hydric,

13. A lubricating composition comprising/a improved by the inclusion therein of a minor proportion of the phosphorus-containing product resulting from the reaction of an ester of apolybasic hydroxy acid with a phosphorus and halogen-containing compound of the type in which the phosphorus is present intri-valent form.

14'. A lubricating composition comprising a major proportion of mineral oil, the properties of which affecting its use as a lubricants-in the crankcase of an internal combustion engine are improved by the inclusion therein of a minor proportion of the phosphorus-containing product resulting from the reaction of an ester of a a saturated poly-basic hydroxy acid with a phosphorus and halogen-containing compound of the type in which the phosphorus is present in tri-valent form.

15. A lubricating composition comprising a major proportion of mineral oil, the properties of which affecting its use as a lubricant in the crankcase of an internal combustion engine are improved by the inclusion therein of a minor proportion of the phosphorus-containing product resulting from the reaction of anester of a low molecular weight saturated poly-basic hydroxy acid with a phosphorus and halogen-containing compound of the type in which the phosphorus is present in tri-valent form.

16. A lubricating composition comprising a major proportion of mineral oil, the properties of which affecting its use as a lubricant in the crankcase of an internal combustion engine are improved by the inclusion therein of a minor proportion of the prosphorus-containing prodhydric alcohol with a phosphorus and halogencontaining compound of the type in which the phosphorus is present in tri-valent form. a 19. A lubricating composition comprising a major proportion of mineral oil, the properties of which afiecting its use as a lubricant are improved by ,the inclusion therein of-from an effective amount to about 1% of an oil-soluble product resulting from the reaction of a hydroxy-ester with a phosphorus and halogen containing compound of the type in which the phosphorus is present in the tri-valent form.

20. A lubricating composition comprising a major proportion of mineral oil which has been stabilized by the inclusion therein of from about .001% to about 2% of an oil-soluble product resulting from the reaction of a hydroxy-ester with a phosphorus and halogencontaining compound of the type in which the phosphorus is present in the tri-valent form.

21. A lubricating composition comprising a major proportion of a lubricating oil the resistance of which to oxidation is improved by the inclusion therein of from about .0l% to about .1% of the product resulting from the reaction of a hydroxy-ester with a phosphorus and halogen containing compound of the type in which the phosphorus is present in tri-valent form. i

22. A composition of matter comprising a major proportion of a liquid hydrocarbon having included in solution therein from an effective amount to about 1% of a compound containing phosphorus in tri-valent state, at least one uct resulting from the reaction of an ester of al low molecular weightsaturated poly-basic hydroxy acid and a monoor di-hydric alcohol with a phosphorus andhalogen-containing compound of the type in which the phosphorus is present in tr'i-valent form.

17. A lubricating composition comprisingv a major proportion of mineral oil, the properties of which affecting its use as a lubricant in the crankcase of an internal combustion engine are improved by the inclusion therein of a minor proportion of the phosphorus-containing product resulting from the reaction of an ester of a low molecular weight saturated poly-basic hydroxy acid and a low moleculanweight monoor di-hydric alcohol with a phosphorus and halogen-containing compound of the type in which the phosphorus is present in tri-valent form.

18. A lubricating composition comprising a major proportion of mineral oil, the properties of which affecting its use as a lubricant in the crankcase of an internal combustion engine are improved by the inclusion therein of a. minor proportion of the phosphorus-containing prodbond of which is attached to the radicle -ORCOOR', where R isan organic radicle and R. is selected from the class consistingof an organic radicle, hydrogen, a metal and a metallic radicle.

23. A composition of matter vcomprising a major proportion of a liquid hydrocarbon which has. been stabilized by the inclusion therein or from about .001% to about .2% of a compound containing phosphorus in -tri-valent state, at

least one bond of which is attached to the radicle --ORCOOR, where R is an organic radicle and R is selected from the class consisting of an organic radicle, hydrogen, a metal and a metallic radicle.

uct resulting from the reaction of an-ester of a low molecular weight saturated poly-basichydroxy acid'and a low molecular weight mono- 24. A composition of matter comprising a major proportion of a liquid hydrocarbon, the

resistance of which to oxidation has been improved by the inclusion in solution therein 01 from about .01% to about .1% of a compound containing phosphorus in tri-valent state, at