US2312208A - Compounded hydrocarbon oil - Google Patents

Description

Patented Feb. 23, i943 No Drawing.

Application April l2, istil,

Serial No. 38,299

25 Claims..

This invention relates to a neur and useful composition of matter comprising a hydrocarbon oil and a salt of organic substituted acids oi boron. More particularly, the invention involves cornpounded oils containing an oxide, sulilde or selenide in which an oxygen, sulfur or selenium atom is directly attached to a metal and a boron atom.

The present invention involves the discovery that dispersion in hydrocarbon oils oi' certain oxides, suldes or selenides containing the group- (A) (X) (B) (R) ln which A represents a salt-forming element or radical, X is oxygen, sulfur or selenium, B is horen, and R is an organic radical, imparts new, unpredictable and desirable properties to the composition. These new proporties render the compounded oil particularly useful for various purposes. Increased resistance to deterioration under oxidizing condi tions comprises one of the principal advantages of the compounded oils of this invention. lout it is to be understood that the invention is not limited to this feature. Dlerent compounds of the gen eral type herein involved vary'in their decree of eectiveness and may impart one or more other desirable properties to the composition. For enample, certain of the compounds may reduce the amount of weer produced inlubrication of metal surfaces as compared with weer resulting with a straight uncompounded lubricating oil. The same or other compounds inhibit corrosion of alloy bearings of the type represented by copperlead or cadmium-silver nearing metals. In general, however, it has been discovered that the new compositions herein disclosed arei more stable to deterioration by heat and oxidation than is ahydrocarbon oil with which the compositions are compounded. The new compounds of this lovention are therefore useful where a stabilized oil is desired and resistance to deteriorationA is impor- Cil (A) (X) (B) (R) as previously identified, :may he regarded as salts or substituted acids ci boron. Metal salts of substituted onyaclds of trivolent boron are preferred compounding agents. Metals preferred as coxn` nonentsfo the salts utilized in this invention are metals selected from groups lil, lil', IW and Vl of Mendeieeiis Periodic Table of the Elements. eine cinc exil-amples oisuch metals are: calcium, stron tium, barium, magnesium, zinc, cadmium, slumi num, zirconium, bismuth, tin, lead, chromium and molybdenum. Salts of iron. cobalt, nickel, mansenese, vanadium, sodium, mtassium, copper and silver comprise additional examples of metals falling within the broader aspects of the invention. Salt-forming radicals such es the ammonhun and amine radicals are not precluded.

The compounds of this invention are preferably formed from substituted onyaoids oi trivalent boron oi the following formulae:

/ Vou n-s \on orsanlc boronic acids;

/s-ou Bl organic borinic acids;

/on n-o-B inonoesters of orthohoric acid;

non

Y diesters of orthobox'ic acid;

cations in an insulating, switch or transformer oil.

Compounds of the bym herein involved and containing the groupwhere R and R' are radicals of hydrocarbon structure.' It is understood that we do not preclude' ingv at least twelve carbon atoms in the-molecule.

However, it is to loe understood that thef broeder aspects of the invention include the use of derivatives of other types of organic substituted acids of boron.

-Additional examples of organic substituted acids of boron which may be used in forming thesalts ofthe present invention are as follows: Y

sn 4 n -B/` \on I organic monothio-boronic acids;

B-B \sH organic dithlo-boronic acids:

\B-sH R organic thio-borinic acids;

R-s-B/ l H monoesters of monothio-organo Tooric acid:

fR-o-B v on monoesters of organo monothio-boric acid:

` R-o-B monoesters of organo dithio-boric acid;

\BH o/ n R/ diesters of monthio-organo boric acid;

\B-sH o/ fR'/ diesters of thio-organo thio-boric acid;

diesters of dithio-organo boric acid:

diesters of dithio-organo tlziio-boricl acid.

In all of the foregoing formulae R` and R' are radicals of hydrocarbon structure. Throughout the specification and claims the term radical of hydrocarbon structure" includes:

(a)-I Alkyl radicals. such. as amyl. isoamyl, hexyl, heptyl, octyl, the isomeric octyls, lauryl,

dodecyl (normal or branched chain), tetradecyl and cetyl (normal or branched chain) radicals: (b) Aryl, such as the phenyl, diphenyl and naphthyl, p radicals;

`(c) Aralkyl, such as phenyloctadecyl and similar alkyl radicals connected to the boron atom and havingan aryl group as a substituent inthe alkylchain;

(d) Alkaryl, such as methylphenyl, cetylphenyl, and other radicals where the aryl g'roup is directly attached to the boron atom and is substituted with an alkyl group;

(e) Cyclic nonbenzenoid radicals, such as cyclohexyl or other alicycllc radicals;

(f) Oxy radicals such as those in which the hydrogen of an hydroxyl group has been replaced by esteriiication, etheriiication, neutralization with a metal, or the like; f

(g) Radicals containing thio, amino, halogen -or other groups.

It should be borne in mind that in the previously listed type formulae all of the acids listed may not exist as such and that it is the salt-like derivatives thereof with which the present invention is concerned. Accordingly, existence of the free acid in a stable form is not a prerequisite to the preparation of the derivatives thereof contemplated herein In general, salts and preferably polyvalent metal salts of organic substituted derivatives of acids of boron, such as orthoboric, HsBOs; mesoboric, H4B2Os; metaboric, HzB204; dihydrodiboric, HiBzOa; hexahydrotetraboric, H6340 (once called pyroboric acid); dihydrotetraboric, HzBiOr; hexahydrohexaboric, HoBsOn; dihydrohexaboric, -HzBeOm hexahydro octoboric, HsBaOns; dihydro-octoboric, HzBsOis; dihydrodecaboric, HzBmOie; and dihydrododecaboric, HzBizOia; fall within the broadest aspects of the invention. By "substituted" or substituted derivatives of acids of boron whenever used herein it is intended to designate acids containing an organic group of the type previously listed, which acidsmay be either an oxy and thio or a mixed oxy and thio acid of boron. The organic groups may be either directly attached to the boron atom of the compound or attached thereto through an intervening atom, such as oxygen or sulfur. The term oxyacid of boron is intended to designate acids in which at least one oxygen' atom intervenes between the hydrogen and boron atom of the parent acid.

Thepreferred acids are substituted acids of trivalent boron and the preferred salts comprise the magnesium, aluminum, calcium, barium, tin, and chromium salts of these acids. Examples of such salts are: magnesium, aluminum, calcium, barium, tin and chromium monododecyl, mono tetradecyl, monocetyl, vmono-octadeeyl, mono- (amylphenyl) mono-decylphenyl) mono-(dodecylphenyl), mono-*(tetradecylphenyl), mono- (cetylphenyl), monon'aphthenyl, dihexyl, dioctyl, didecyl, didodecyl, ditetradecyl, dicetyl, dioctadecyl, diphenyl, dbenzyl, di-(ethylphenyl), di- (amylphenyl), di-(decylphenyl), di-(dodecylphenyl), di-(cetylphenyl) and di-(cyclohexyl). borates; magnesium, aluminum, calcium,- barium, tin and chromium dodecyl, tetradecyl, cetyl, octadecyl, amylphenyl, decylphenyl, dodecylphenyl, tetradecylphenyl, cetylphenyl and naphthenyl, boronatcs;l and magnesium, aluminum, calcium, barium, tin and chromium dihexyl, dioctyl, didecyl, didodecyl, ditetradecyl, dicetyl, dioctadecyl, diphenyl,. dibenzyl, di- (ethylphenyl) di-(amylphenyl) di- (decylasiaaos phenyl), ril-(dodecylphenyl) phenyl), borinates.

The substituted acids of boron utilized in the preparation oi lthe salts of this invention mai7 be obtained by known methods. For example. the monoesters of boric acid and diesters oi boric acid are obtainable by hydrolysis of the triester, and the desired salts maybe prepared from and di-(cetyleither the menti-alizee partially hydrolyzed ester or from the sodium salt thereof by reaction with the desired metal ion.

The 'diesters of boronic acids areobtainable, for example, by the slow omdation of trialkyl borine. Also, the aliphatic and aromatic boronic acids can be prepared readily by the reaction of Grignard 'reagents upon alkyl esters of boric acid or the etherate oi boron triuoride instead of analkyl borate.

In general, it may be explained that boricA of boron. Alkyl boronic acids in general may be prepared by this procedure without essential modication:

A 1-liter 3-necked ask is tted with an eilicient mercury sealed stirrer and one neckV provided with a low temperaturethermometer and a glass tube for the introduction of nitrogen. The remaining neck carries a 590 cc. separatory funnel and an outlet tube for nitrogen or other inert gas. The nitrogen outlet tube and the top of the separatory funnel are connected to two arms of a Y-tube, the third arm of which is sealed by a mercury valve. Dry nitrogen, puried. over sulfuric acid and alkaline pyrogallol, is allowed to now through the apparatus -for about twenty minutes. Then' 55 grams (0.53 mol) of pure methyl borstels added quickly through the separatory funnel and washed through with 150 cc. oi anhydrous ether. The flask is suspended in a Dewar dish containing a mixture of acetone and solid carbondioxide and the solution stirred. during cooling. internal temperature has fallen to about 75", 360 cc. (0.5 mol) of alkyl magnesium bromide solution (1.66 N) is introduced slowly through the separatory funnel over a period of several hours. The new of nitrogen and vigorous stirring are maintained during the addition and the temperature held below 70% During the addition a voluminous precipitate separates. When the addition is complete, the mixturels stirred at 70 for several hours and allowed to stand in' the cooling bath over night to insure completion of the reaction. The as'n is then opened momentarily and the cake of precipitate broken into small amounts. The. apparatus is reassembled and 360 cc.- of water containing 30 cc.

of sulfuric acid added with stirring and cool ing. The ethereal layer is separated and the aqueous layer extracted with u cc. of ether.

The extract is combined `with the main ether' layer. The ethereal solution is concentrated on a steam bath and distillation continued until all When the is removed. The acid which separates upon cooling the residual liquid is ltered with suction and may be dried in a nitrogen-filled desiccator over sulfuric acid. This crude acid may be puried by warming with 275 cc. of toluene, the solution ltered at 60 C. and chilled thoroughly to cause crystallization.

The necessity for maintaining extremely low temperatures, as in the above method, may be avoided by using a less volatile ester as a starting material, for example, by using n-butyl borate.

Example 2.-n-Tetradecanol is converted to the bromide (B.- P.l32i35 F. at 2 mm.). The Grignard reagent from this bromide is added to n-butyl borate and gives a crude impure acid contaminated with the hydrocarbon Cisl-15s. The

.latter may be removed by dissolving the crude acid in 95% alcohol and chilling. The puriiled n-tetradecane boronic acid is obtained by evaperation of the alcohol and crystallization from petroleum ether.

Example 2.-Cetyl alcohol is converted to the bromide. The Grignard reagent from this bromide is added to a suitable box-ate ester such 'as the n-butyl hor-ate.

Example 3.-Phenyl magnesium bromide is added to n-butyl borate to obtain the benzene boronic acid as in the foregoingexamples.

Example d Cetylphenylrn'agnesium bromide obtained from cetyl benzene may be used to prepare cetylphenyl or cetyl benzene boronic acid.

as previously indicated, salts of the foregoing acids may be prepared by treating the acidY with aqueous alcoholic sodium hydroxide and then precipitating the various salts by adding an aqueous solution containing the desired metal ion. For example, cetyl boronic acid is reacted with aqueous alcoholic sodium' hydroinde to give sodium cetyl boronate from which. various salts are prepared as follows:

Example 5.--Aqueous calcium chloride is added to the aqueous alcoholic solution of sodium cetyl boronate to precipitate calcium cetyl boronate. The precipitate is ltered, washed and dried, or it may be taken up immediately upon precipitation by dissolving in an organic solvent such as a hydrocarbon mineral oil..

Example 6.-10 prepare the zinc salt, aqueous zinc chloride solution is added to the alcoholic sodium cetyl boronate solution.

Example 7.-'I'o prepare the magnesium salt, aqueous magnesium chloride or magnesium sulfate solution is added to the alcoholic sodium cetyl boi-ouate solution.

Example 8.-To prepare the aluminum salt. aqueous aluminum chloride or aluminum sulfate solution is added to the alcoholic sodium cetyl boronate solution.'

Example 9.-'10 prepare the tin salt, aqueous tin. chloride solution is added to the alcoholic sodium cetyl boronate solution.

Example Ill-To prepare the lead salt, aqueous 4 v lead acetate solution is added to the alcoholic sodium cetyl boronate solution.

Example 11 .-To vprepare the chromium salt, aqueous chromic sulfate or chrome alum solution is added to the alcoholic sodium cetyl boronate solution.

Eample 12.-'l`o prepare the manganese salt, aqueous manganese sulfate solution is added to the alcoholic sodium cetyl boronate solution.

material volatile at the temperature of the bath Example 23.-To prepare the nickel salt, aque- Y ous nickel chloride solution is added to the alcoholic sodium cetyl boronate solution.

Example I-To prepare the cobalt salt, aque# A borinic acid is obtained when boron djphenyl chloride or bromide is treated with sodium hydroxide and the clear solution neutralized with hydrochloric acid. The dibenzene borinic acid results and readily forms alkali metal salts which in turn may be converted to a polyvalent metal salt by reaction with the desired metal ion.

Salts of the partially esteriiled boric acids may be prepared by partially hydrolyzing the ester with sodium hydroxide to obtain the sodium salt of the partial ester. Other salts may be precipitated by double decomposition in accordance with the methods described in the foregoing examples.

Among the benefits which may be derived from the incorporation of the compounds of this invention in lubricating oils. are inhibition of corrosion of bearing metals and increased stability of the oil as indicated by lower neutralization number and lower A. S. T. M. naphtha insolubles after use. Table I gives data illustrating these properties.

In the tests whose results are summarized in Table I, thi-n sheets of the indicated bearing metals were cut into strips (copper-lead, 19;" x 1%" x 2535"), and these Ystrips were immersed in the exemplified oils carried in 2" x 20" glass test tubes; these test tubes were carried in an oil bath maintained at 300 F. :1 F. Each test tube contained approximately 300 cc. of oil, and air was bubbled through each tube at the rate of l liters per hour. At the end of each of three 24-hour periods, the strips were removed from the oils, washed With petroleum ether and carefully wiped with a soft cotton cloth; weight losses of the strips were measured in connection with the weight of each individual strip. The

Among the beneficial effects which flow from the incorporation of the above-described compounds in a hydrocarbon oil of the lubricating oil class is the prevention of piston ring sticking, or its marked postponement, under very severe motor conditions, as for example in Diesel engine or in aircraft spark or compression ignition engine operations.

f Table II Piston discoloration number Hours to Ol stick rings Acid rened S. A. E. 30 naphthenc base 45 Poor.

oil. Acid refined S. A, E. 30-naphtbenic base &0

ol+0.35% calcium cetyl boronate.

Improved.

In the tests whose results are summarized in Table II, a single cylinder Lauson gasoline sparkignition engine, 2%"- bore and 2%" stroke.

the operations were interrupted and the condif tion of the piston rings determined.

Additional examples of acids4 of boron, the

salts of which are contemplated as addition agents for hydrocarbon oils within the broadest aspects of the invention, are as follows: p-chlorophenyl boronc acid, p-'bromophenyl boronic acid, o-anisyl boronic acid, o'phenetyl bororic acid, and o-xylyl boronic acid. The calcium, strontium, barium, magnesium, zinc, cadmium, aluminum, zirconium, bismuth, tin. lead, 'chromium, molybdenum, iron, cobalt, nickel, manganese, vanadium, sodium, potassium, copper and silver salts of these acids may be utilized.

Reference has previously been made to the fact that amine salts of the acids disclosed in the speciiication fall within the broader aspects of the invention. Examples of suitable amines are the alkyl amines, such as triethyl amine;l

the alkylol amines, like triethanolamine; and

the aromatic amines, such as aniline. Nitrogen` bases obtained from petroleum, ,and especially reduced nitrogen bases such as homologues of piperidine, are also included as an amine with which the salts of this invention may be made.

The proportion of the addition agents herein disclosed which may be added to hydrocarbon oils according to the principles of the present invention may vary widely, depending upon the uses involved and the properties desired. As

little as 0.05% bygweight of various of the compounds gives measurable improvements. Fromapproximately 0.1%- to 2% of the compounds may be added to lubricants where enhanced stability under oxidizing conditions is desired. More than 2% of the compounds may be utilized for various purposes, e. g. for preparing lubricating greases and concentrates capable of diluto encounter. 'It shouldv be observed, for example, that even though a compounded oil may be somewhat corrosive to copper-lead or cadmium-silver bearing metals, Babbitt bearings may be little if at all aifected by such corrosive action. Hence, compounded oils which maynot -be particularly desirable for lubrication of copper-lead or cadmium-silver bearings at high temperatures wherevcorrosion becomes a factor of importance may be highly useful and extremely advantageous in conjunction with operations where bearings of Babbitt or other .corrosiveresistant bearing metals are utilized. Likewise, compounded oils in which the addition agent is not sufficiently powerful to stabilize the oil against deterioration by oxidation under the most severe conditionsmay be highly useful in escasos may not be so high.

In the preparation of either the nished oils of the invention or the bases or concentrates referred to, complete or clear and homogeneous solution is not always necessary. Blending agents or homogenizers may be employed, if desirable, to prevent sedimentation of the less oilsoluble agents bui-I it has been found that the possible detrimental eect of the presence of lterable insoluble materials of this character, if present, is determined largely by the particular conditions attending the contemplated use and that with those addition agents of limited oilsolubility the presence of. additional oil-insoluble agents is not in all cases deleterious to the function of the compositions in their intended manner.

The preferred hydrocarbon oil is a mineral lubricating oil fraction such as a moderately acid rened naphthenic :rase lubricating oil. Other base oil stocks for the compounded oils involved `herein may be utilized, e. g. 'paranic oil stocks or highly refined naphthenic oils, as Well as synthetic hydrocarbon oils. It is to be understood that the broader aspects of the invention are not limited to any particular base stock since the advantages herein disclosed may be obtained, at least to some degree, 4with various oils, the selection oi which will be determined by conditions and service which the product is to encounter.

The addition agents or this invention may be utilized in hydrocarbon oils containing other compounding agents, such as pour point depressants, oiliness agents, extreme pressure addition agents, blooming agents, compounds for enhancing the viscosity index of the hydrocarbon oil, and auxiliary stabilizing agents such as metal alcoholates, metal salts of phenols containing organic substituents and the like. Further, thickening agents and/or meta-l soaps in greaseforming proportions or in amounts insucient to form grease may be utilized in combination with the addition agents of this invention.

While the character of the invention has been described in detail and numerous' .examples of the compounds given, this has been done by way of illustration only and with the intention that no limitation should be imposed upon the invention thereby. It will be apparent to those skilled in the art that numerous modifications and variations of the illustrative examples may be eiected in the practice of the invention which is of the scope of the claims appended hereto.

We claim:

l. A composition comprising a hydrocarbon oil containing a small amountof a salt of a substituted acid of boron containing an organic substituent. said small amount being at, least about 0.05% by weight.

2. A composition comprising a hydrocarbon oil containing from' about 0.1% to about 2% by weight of a metal salt of a substituted acid of boron containing an organic substituent.

S. A oil cont l weight of a acid of boron containing an organic substituent.,

e. A composition comprising` e. hydrocarbon oil'con from about 0.1% to about 2% by weight of an ammonium salt oi a substituted acid of boron containing an or =-.I c substituent. Y 5. A composition comp a hydrocarbon oil cont from about 0.1% vto about 2% by weight of an amine salt of a substituted acid of boron containing an organic sutuent.

6. A composition comprising a hy arbon oil and from about 0.1% to about 2% by weight of a compound con the group- (A) (x) (e) (a) in which A is arnet-a1, X is selected from the group consisting of oxygen; sulfur and selenium.

Bis boron, and R is an organic radical.

7. A composition as dened in claim 6 in which y A is a polyvalent metal.

8. A composition comprising a hydrocarbon oil and at least about 0.05% by weight of a salt of an acid ester of an acid of boron.

9. A composition comprising a hydrocarbon oil and at least about 0.05% by weight of a metal salt of an acid ester of an acid of boron.

l0. A composition comprising a hydrocarbon oil and at least about 0.05% by weight of a polyvalent metal salt of an acid ester of an acidi3. A composition comprising a hydrocarbon oil. and from about 0.1% to about 2% by weight of a salt of an organo-borchie acid.

14. A composition comprising a hydrocarbon oil and from about 0.1% to about 2% by weight of a salt of an organo-bormio acid.

l5. A composition comprising a hydrocarbon oil and from about 0.1% to about 2% by weight of a salt of an orthoboric acid containing an organic substituent.

i6. A composition comprising a hydrocarbon oil and from about 0.1% to about 2% by Weight of a salt of a dibasic orthoboric'acid containing an organic substituent. .Y

l?. A composition comprising a hydrocarbon oil and from about 0.1% to about 2% by weight of a salt of a monobasic orthoboric acid containing an organic substituent.

18. A compounded lubricant comprising a lubricating oil subject to deterioration at elevated temperatures and a salt of an acid of boron containing an organic substituent, said salt being present in an amount suicient substantially to inhibit said deterioration.

l0. A compounded lubricant comprising a lubricating oil subect to deterioration at elevated temperatures and a metal salt of an acid of boron containing an organic substituent, said salt being present in an amount suucient substantially to inhibit said deterioration.

20. d compounded lubricant comprising a lubricating oil subject to deterioration at ele voted temperatures and a polyvalent metal sait of an acid of boron containing an organic substituent, said salt being present in an amount sumient substantially to inhibit-said aet'erio tion.f. s 21. A compounded lubricant comprising a hydrocarbon oil with'the properties ot auch 'compositio!! affecting its use as a lubricant improved by incorporatinrtherein at least 0.05% by weight based on the oil of a sait-ot an acid oi'bo'ron containing an organic substituent.

22. A compounded lubricant as defined in claim 21, in which saidvsalt isa polyvalent metal.

based lon the oil oi.' a saltjoi an organicv acid ester oi an acid'of boron.

an organic substituted boron compound. said concentrated solution containing more than 2% by'weight based onthe oil of said saltand'beins deterioration of lubricating oils which comprises :4.4m addition sgent'oapable of inhibiting deterioration ot lubricating oils whichl comprises a.I concentrated solution in oil'ot il.V salt oi capable of dilution with mineral lubricating -oil to form a homogeneous mixture containing trom approximately 0.05% to 2% by weight of said 25. An addition ase'nt capable of inhibiting a concentrated solution in oil oi' a polyvalent metal salt of an acid ot boron containing an organic substituent. said concentrated solution containing more than 2% by weight based on Y the .oil of said salt and being capable of dilution with mineral lubricating-oil to form a-homogeneous mixture containing' from approximately 0.05% to 2% by'weight of said salt.

JAMES o. CLAYTN. -BRUCE B. FARRmGToN.