US2228659A - Compounded mineral oil - Google Patents

Description

Patented Jen, as, ten

NITED STATES COMPOUNDED MINERAL on.

Bruce B. Fan-ington, James 0. Clayton, and John "1. Rutherford, Berkeley, Calif., asslg-nors to Standard Oil Company oi California, San Francisco, Calif., a corporation of Delaware 1N0 Drawing. Application November 21,1938, Serial N0. 241,648

31 Claims.

This invention relates to a new and useful composition of matter and involves a composition comprising a viaashsbs'drocarbon oil and polyvalent metal salt of pertain substituted acids of 5 phosphorus.

The production of improved hydrocarbon oils and particulariytef }lubricating oils having desired characteristics )has been the subject of extensive research andinivestigation in recent years. Generally speaking, the compounding of hydrocarbon oils to obtain desired characteristics involves empirical phenomena and the action of untested types of compounding agents cannot be predicted.

temperatures and severe operating conditions. A

direct result of this iizygie of deterioration during lubrication of internal \camb'ustion engines, such as engines of .the llfliesel type, is the tendency of the oil to causenrgpemiit athe sticking of piston rings.

The crankcase ilibiiica-nt in internal combustion enginesiissubiented to extremely severe operatingconditions and in (engines of the Diesel type the'lubricant encounters in the piston ring zone temperatures :of from approximately 425 to 650 F. and mm the oxidizing combustion-gasestasihighsasilifl to 1150 lbs. per sq. in. Addition agents which render hydrocarbon oils resistant to tdeieniolzation by heat at high temperature levelsiin "the :order of those above mentioned usuallyiimpart .tothe oil the ability to inhibit piston ringsticking in internal combustion engines and pemfitllonser periods of operation of such engines'without the necessity of major overhaulsFherdtdioixe occasioned by stuck piston rings.

It should "'be that stabilizing agents which are effective tat 110w temperatures to impart increased stabiiitytto hydrocarbon oils, or which are .eifective .at temperatures even as high as 200 or 250 F., are often ineifective under the more severe operating conditions and higher temperature ilevels .to which lubricating oils are subjected iniDiesel engines. Thus the operativeness of astabilizer tatiatmospheric temperatures, or even temperatures .as high as 200 to 300 F,, gives no ademmte thesis zfor predicting the action of the samesitabiliaing agent at materially higher temperatures and under more severe operating conditions. The disclosures in the prior art relative to such stabilizers therefore cannot serve as a guide for one seeking stabilizing agents or oxidation inhibitors effective at higher temperature levels. The phenomena involved are catalytic in nature, are highly empirical and require extensive experimentation to determine the action of a given type of addition agent.

The present invention involves the discovery that dispersion of polyvalent metal salts of substituted oxy acids of phosphorus in hydrocarbon oils such as mineral lubricating oil imparts new, unpredictable and highly desirable properties to the composition. These new properties render the compounded oil particularly useful for vari ous purposes. Although increased resistance to deterioration at high temperature levels comprises one of the principal advantages of the compounded oils of this invention, it is to be understood that the invention is not limited to this feature, that different compounds of the general type herein involved vary in their degree of effectiveness and may impart one or more other desirable properties to the lubricating composition. For example, certain of the compounds reduce the amount of wear produced as compared with a straight uncompounded mineral oil. The same orother compounds inhibit the corrosion of copper-lead or cadmium-silver hearing metals, etc. In general, however, it has been discovered that the new compositions herein disclosed are more stable to heat than is a hydrocarbon oil with which the compositions are compounded. The new compositions of this invention are therefore useful where resistance to deterioration by heat is important. An example of such utility, other than as a lubricating oil, comprises use as a heat transfer fluid where it may be desirable to inhibit or prevent the formation of a deposit on the metal surfaces from or to which heat is being conveyed. Likewise, the increased resistance to oxidation imparted to the oil by the compounds of this invention will find various applications as, for instance, in an insulating, switch, or transformer oil.

It has also been discovered that certain metal salts of substituted oxy-phosphoric acids have a combination of properties heretofore unknown and particularly desirable in compounded mineral oil, namely, the ability to inhibit oxidation and impart to lubricating Oils increased resistance to deterioration by heat, the ability to inhibit piston ring sticking, freedom from the production of increased wear on cylinder walls and piston rings as compared with uncompounded mineral oils, and low corrosivlty as respects the chemical action of the compounded oil on hearing metals such as cadmium-silver and copperlead alloys. Although various compounded minaluminum, calcium, barium, strontium, chromium and magnesium. Salts of iron, cobalt, nickel, zinc, tin and lead comprise additional examples of compounds falling within the broader aspects of the invention.

The metal salts of this invention are preferably formed from substituted oxy acids of pentavalent phosphorus of the following type formulae:

where R and B may be alkyl, aryl, alkaryl, aralkyl or cyclic non-benzenoid radicals. Substituted phosphoric acids containing at least twelve carbon atoms are preferred. Examples of preferred type acids are alkyl or alkaryl substituted phosphoric acids having at least twelve carbon atoms in the molecule. However, it is to be understood that the broader aspects of the invention include the use of other types of substituted oxy acids of phosphorus containing more than twelve carbon atoms. Additional examples of substituted oxy acids of phosphorus which may be used in forming the metal salts of the present invention are as follows:

Phosphonic acid Mono-ester of phosphonlc acid;

Phosphinic acid In all of the above formulae R and R. may be alkyl, aryl, alkaryl, aralkyl or cyclic non-benzenoid groups.

In general, polyvalent metal salts of substituted derivatives of oxy acids of phosphorus such as phosphorous acid, hypophosphoric acid, HaPOa; orthophosphoric acid, H3PO4; pyrophosphoric acid, 114F207; fall within the broadest aspects of the invention. By "substituted" or "substituted derivatives of" acids of phosphorus whenever used herein, it is intended to designate acids containing an organic group of the type previously listed, 1. e., alkyl, aryl, alkaryl, aralkyl, or cyclic non-benzenoid groups. The organic groups may be either directly attached to the phosphorus atom of thecompound or attached thereto through an intervening atom such as oxygen. The term "oxy acids of phosphorus is intended to designate throughout the specification and claims acids of phosphorus in which one oxygen atom may intervene between the hydrogen and phosphorus atoms of the ester.

The preferred acids are substituted orthophosphoric acids and the preferred salts comprise the aluminum, calcium, barium and chromium salts of these acids. Examples of such salts are aluminum lauryl phosphate, aluminum cetyl phosphate, aluminum octadecyl phosphate,-aluminum "spermol" phosphate, aluminum oleyl phosphate, aluminum spermenyl" phosphate, aluminum cetyl phenyl phosphate, aluminum di-(amyiphenyl) phosphate, aluminumnaphthenyl phosphate, calcium lauryl phosphate, calcium cetyl phosphate, calcium octadecyl phosphate, calcium spermor'phosphate, calcium oleyl phosphate, calcium spermenyl" phosphate, calcium cetyl phenyl phosphate, calcium dlJa'mylphenyl) phosphate, calcium naphthenyl phosphate, chromium lauryl phosphate, chromium cetyl phosphate, chromium octadecyl phosphate, chromium "spermor phosphate, chromium oleyl phosphate, chromium spermenyl" phosphate, chromium cetyl phenyl phosphate, chromium di-(amylphenyl) phosphate, chromium naphthenyl phosphate, barium lauryl phosphate, barium cetyl phosphate, barium octadecyl phosphate, barium spermol phosphate, barium oleyl phosphate, barium spermenyl" phosphate, barium cetyl phenyl phosphate, barium di-(amylphenyl) phosphate, and barium naphthenyl phosphate. I

Additional examples of'salts within the scope of the invention are: aluminum di-cyclohexanyl phosphate, aluminum di-stearo-glyceryl phosphate, aluminum tetra-chloro-octadecyl phosphate, aluminum di-(6-chloro, 2 -phenyl phenyl) phosphate, aluminum di;( 3,-methyl, 4-chloro phenyl) phosphate, calcium di-cyclohexanyl phosphate, calcium di-stearoglyceryl phosphate, calcium tetra-chloro-octadecyl .lfllosphate, calcium di-(6-chloro, 2-phenylphenyl) phosphate, calcium di-(3-methyl, 4-chloro phenyl) phosphate, chromium di-cyclohexanyl phosphate, chromium di-stearo-glycerylphosphate, chromium tetra-chloro-octadecyl phosphate, chromium di- (6-ch1oro, 2-phenyl phenyl) phosphate, chromium di-(3-methyl, 4-chloro phenyl) phosphate, magnesium dicyclohexanyl 3 phosphate, magnesium di-stearo-glyceryl ;-phosphate',';,magnesium tetra-chloro-octadecyl phosphata magnesium di- (6-chloro, 2-.phenyl phenyllgphosphate. m nesium di-(3-methyl, 4-chloro phenyl) phosphate, magnesium lauryl phosphate, magnesium cetyl phosphate, magnesium-,octadecyI phosphate, magnesium spa 'mol",phosphate, magnesium oleyl phosphate, magnesium "spermenyl'? phosphate, magnesium cetyl phenyl phosphate, magnesium di-(amylphnyl) phosphate, magnesium naphthenyl phosphate, barium di-cyclohexanyl phosphate, barium. di-stearo-glyceryl phosphate, barium tetrachloro -octadecybiphos+ phate, barium di-(fi-chloro,12 pheny1mphenyl) phosphate, and barium -di-(3-methyl,'sl chloro phenyl) Phosphate.

The substituted oxy acids of ph'csphorusuti- 2,22e,eee

is believed to be represented by the iollowing equation:

tion.

' Table 1 Acid Method of preparation Mono-cetylphosphoric 0% lb. eetyl alcohol and 5.61 lb.

PaOi were refluxed with 5 gal. ethyl ether for 24 hr. Cetylphosphoric acid solution decanted.

112 gnis. solid sperm alcohols, 60 gins. P208, and 400 gins. ethyl ether treated as above.

Mcno-spermol phosphoric...

Mono-octadecylphosphoric--.. gms. octadecanol and c. c.

benzene treated with 56.8gms.

P0011. Product was hydrolyzed to give a free acidic hyd gen.

Di-(o chloro-z-phenyl-phenyl) 100 gins. ot the phenol and 50 g'ms.

phosphoric. P10: heated to for-ls houis.

Mono-oleylphosphoric l0! gins. oleyl alcohol and 28.5 gms.-

P10; were refluxed in ethyl ether ior 24 hours.

107 gins. li uid sperm alcohols and 27 gins. :0 refluxed in ethyl Micno-spermenyP phosphorether for 24 hours.

(Cetylphenyl) phosphoric. 688 gms. eetyl phenol and 316 gms Pros refluxed with ethyl ether ior 24 hours.

Di-(amylphenol) phosphoric... 100 gins. amyl phenol and 43 gins.

Mono (tetrachloro) octadecylgms. tetrachloro-octademnol phosphoric.

and 28 gins. PaOs refluxed with ethyl ether for 17 hr.

In preparing'the metal salts herein involved,

the ethyl group in the ethyl phosphoric acid above mentioned may be hydrolyzed oil? to form the metal salt of the mono-alkyl-ortho-phos- PiOs heated to 185 F. for 16 hr.

of operation is not limited to the alkyl derivatives but includes aryl-ethyl-phosphoric acid, alkaryl-ethyl-phosphoric acid, aralkyl-ethylphosphoric acid and ethyl phosphoric acids containing a cyclic non-benzenoid group.

The metal salts of the various substituted oxy acids of phosphorus may be conveniently prepared by reacting the acid with sodium hydroxide or potassium hydroxide and then precipitating the desired metal salt from the solution of the sodium or potassium salt by the addition of the appropriate metal ion. The salt may also be prepared by the direct neutralization of the acid as, for example, with lime where the calcium salt is-to be obtained.

Basic aluminum salts prepared by the precipitation method are preferred by reason of their low corrosivity to alloy bearing metals although the so-called normal salts are not precluded. It is also preferred to maintain the amount of coprecipitatedalkali metal'salt in the heavy metal compounds at a minimum because the alkali metal salts decrease the stability of the oil solution in the presence of water.

The calcium salts may also be prepared in the non-aqueous environment by the reaction of calcium carbide with the free substituted acids of phosphorus.

The aluminum salts may also be prepared in an environment substantially free of water by the reaction of aluminum chloride with the free substituted acids of phosphorus. However, such aluminum salts have properties different from the salts prepared by precipitation from aqueous solutions. The salts prepared in a non-aqueous environment are soft, low melting solids, while the corresponding salts prepared by precipitation from aqueous solutions are hard, non-melting solids. Although the former type of salt may be utilized for imparting some desirable properties to hydrocarbon oils, itis preferred to use a salt prepared by precipitation-from aqueous solutions 7 where the ability to inhibit piston ring sticking in lubricating oils is desired.

By way of illustration and to demonstrate'the unique properties possessed by the compounded oils of this invention, data from extensive tests phoric acid, 1. e. the salt of RH2PO4. This type are given in Table 2.

Table 2 Engine tests Miscellaneous tests Preparation oi compound Lauson Strip corrosion Weeks Compound Ring Viscosity machine, Salt preof stick- Cleanliness Cu-Pb Od-Ag increase wear, Acid pared 38" in! 100 F. 300 F. from- Acid treated Western oil---.. 0 1.0 Poor.----. 1.0 1.0 417 1.0 Aluminum lauryl phosphate. 1. 0 5. 0 Good- .0. l 1. 5 v 546 Oomgiercial lauryl phosphoric Na salt.

sci

Do 0. 05 '0. 1 0 do Aluminum cetyl phosphate. l. 6 5. 0 Very good. 450 Cetyl alcohol-l-Pzo -l-ether Do 0.1 4.0 Good 0.2 0.7 161 -do D 0.8 v 5:}: ---do 0.6 0.7 146 do Alufiggum octadecyl phos- 0. l5 5. 0 Very good 0. 1 l. 0 Octadecyl alcohol+P0Cl e a. Al %itgum "spermol" phosl. 0 5. 0 do Low 4. 0 solijxli1 sperm alcohols-{$20 Do.

. e or.

p Do 0.7 5.0 -do 1.0 1.0 211 do Do. Aluminum oleyl phosphate 0. 7 4. 0 G 0. l l. 0 Oleyl alcohol+P:O5+ethcr. Do. Aluminum spermenyY' 0. 3 2. 0 Fair 0. l 0. 2 Liquid sperm aic0hol+PzO Do.

phosphate. ether.

(l) Expressed as ratio of time to stick rings of compounded oil to that with an nncorrigunded Western acid refined oil S. A. E. 30. (2) Expressed as ratio oi compounded oil corrosion to corrosion with Western acid ed oil 8. A. E. 30.

(3) Expressed as ratio of wear of compounded oil to that oi Western acid refined oil 8. A. E. 30.

The base oil used for testing the addition agent was in all cases an acid refined Western oil 8. A. E. 30 grade.

Table 2-continued Engine tests Miscellaneous tests Preparation of compound Lauson Btrip corrosion d P Weeks Compmm Ring Viscosity machine. Salt rcstick- Cleanliness Cu-Pb Cd-Ag increase K Acid par d ing 100 F. fromsalt Alugningnt di-cyciohoxanyl 0.1 Verygood. "m.-. Cyclohexanol+P0r+ether Nasalt.

us as. .alerlrlnigrlilgimdi-(amyi-phenyl) 1.0 3.0 Fair 0.5 2.0 131 Amylphenol+Pr0 Do.

cap 0 Augnimliim di-stearoslyceryl 0.7 2.0 Gis eryl distearate+Pg0r+ D0.

0s a e Ci slciu ilaurylphosphaie... 1.0 2.0 Fair.. 1.0 6.0 Commercialiauryl phosphoric Do.

C ciumoet i hos hate..... 0.6 6:i: Excellent- Get laicohol PO etherm, K salt, 81 o 33... 0.9 4=e Verygood. 0.5 1.0 do'. Do. Chromium cetyl phosphate- 0.8 ...d0 0 3 0.2 .....do Na salt 0 1.0 5.0 .--d0 d0 D0, Msgnesiumiaurylphosphate. 1.0 2.0 air 0.0 .0 Commercial lauryi phosphoric Do.

a Aluminumleurylphosphite.. 0.3 1.0 do 0.1 0.6 Laurylalcohol+PCis Do.

(I; Expressed as ratio oi timeto stick rings oi compounded oilto that with an uneompounded Western acid refined oil S. A. E. 30. (2 Expressed asratio of compounded oil corrosion tooorrosion 30.

(3) Expressed as ratio oi wear of com unded oil to the with Western acid refined oil 8. A E t oi Western acid refined oil A E 30. The base oil used ior testing the add tion agent was in all cases an acid refined Western oil 8. A. E. 30 grade.

The above data show that small amounts of most of the addition agents act as corrosion'inhibitors even in acid treated Western oils which are ordinarily considered non-corrosive. Likewise, extremely low wear rates were obtained with the two compounded oils tested in the Weeks machine. All of the addition agents improved piston cleanliness and imparted resistance to piston ring sticking in engine tests.

In the above piston ring sticking tests a single cylinder 2% inch bore, 2 inch stroke Lauson gasoline engine was operated under extremely severe conditions for the purpose of developing fully piston ring sticking and piston summing tendencies under circumstances simulating severe operating conditions encountered in the field. Operation of the motor during tests was continuous at 1600 R. P. M. except for shutdowns at fifteen-hour intervals for inspection. The jacket temperature was maintained at 375 F. and the sump oil temperature at 220 F.

The wear tests were carried out in a Weeks machine comprising a inch steel ball pressed against a 1% inch steel cylinder with a. force of 40 lbs., the cylinder dipping in the oil to be tested and rotating at 600 R. P. M. The duration of the test was sixteen hours and the wear rate determined by measuring the amount of metal removed from the ball. In the above wear tests the lubricant was maintained at app'rErimately 300 F. as indicated.

The corrosion tests were carried out in the following manner: Glass tubes 2 inches in diameter and 20 inches long were immersed in an oil bath, the temperature of which was automatically controlled to within 11 F. of the test temperature which was 300 F. Approximately 300 c. c. of oil under the test was placed in each tube and air was bubbled through it at the rate of liters per hour. Strips of the different types of bearing metals were cut to size and placed in the oils; in most cases the copper-lead mixture and cadmium-silver bearing alloys were tested simultaneously. in the same sample of oil. The weight loss of each strip was recorded. Before weighing, each strip was washed in petroleum ether and carefully wiped with a soft cotton cloth. The duration of the test was 72 hours.

To further illustrate the corrosion inhibiting properties of the compounding agents herein disclosed, the following data obtained in the above type strip corrosion test are given: v

The compounding agents herein disclosed may have one or more advantages, depending upon the particular compound selected, the proportion utilized, and the environment which the lubricating oil is to encounter. It should be observed, for example, that even though a compounded oil may be somewhat corrosive to copper-lead or cadmium-silver bearing metals, Babbitt bearings are little if at all affected by such corrosive action. Hence. compounded oils which may not be particularly desirable for lubrication of copper-lead or cadmium-silver bearings may be highly useful and extremely advantageous in conjunction with the operation of internal combustion engines having bearings oi Babbitt or other corrosive-resistant bearing metals. The present invention in its broader aspects is therefore not limited to the use of a particular compound having all or the greatest number of advantages, but embraces various of the less advantageous addition agents which will find utility in particular applications where all the possible improvement in properties may not be required or where the standard of performance may not be so high.

Present experience indicates that where the properties desired involve the ability to stabilize lubricating oils under severe operating conditions, such as those encountered in the lubrication of pistons and piston rings of internal combustion engines of the Diesel type, polyvalent metal salts of substituted oxy acids of pentavalent phosphorus containing more than twelve carbon atoms in the molecule and preferably containing an alkyl or alkaryl substituentshould be utilized.

It is to be understood that by polyvalent metal salts used in theabove connection the alkaline earth metals are included.

A moderately acid refined Western naphthenic base oil is the preferred oil stock used as a base for the compounded lubricants'involved herein. The compounding ingredients appear to function more efliciently in such a base 011 than in a highly paraffinic 011 stock or a highly refined Western 011. However, it is to be understood that the invention is not limited to any particular base'stock' since advantages herein disclosed may be obtained at least to some degree with various oil stocks, the selection of which will be determined. by conditions and service which the compounded lubricant is to encounter.

The proportion of metal salts of substituted oxy acids of phosphorus added to mineral'lubricating oils may vary widely depending upon the uses involved and the properties desired. As little as 0.05% by weight of the compound gives measurable improvements, particularly as respects the color of the compounded oil after use in internal combustion engines. From approximately 0.25 to approximately 2% of the compound may be added to lubricants where ability to inhibit piston ring sticking comprises the principal property desired. Solutions containing more than 2% of the compounds in mineral oil may be utilized for the purpose of preparing lubricating greases and concentrates capable 01' do dilution with lubricating oils and the'like. Such higher concentrations comprise a convenient method of handling the compounds and may be used as addition agents for lubricants in general as well as for other purposes.

M The metal salts of this invention may be added to hydrocarbon oils containing other compounding ingredients such as pour point depressors,

oiliness agents,"extreme pressure addition agents, blooming agents, compounds for enhancing the viscosity index of the hydrocarbon oil, corrosion inhibitors, color stabilizers, etc. The invention in its broader aspects embraces mineral hydrocarbon oils containing, in addition to metal salts 55 of the substituted acids of phosphorus, thickening agents and/or metal soaps in grease-forming proportions or in amounts insufiicient to form greases, as in the case of mineral castor machine oils or other compounded liquid lubricants,

60 While the character of the invention has been described in detail and numerous examples of the composition given, this has been done by way of illustration only and with the intention that no limitation should be imposed on the invention thereby. It will be apparent to those skilled in the art that numerous modifications and variations of the illustrative'examples may be efiected in the practice of the invention which is of the 70 scope of the claims appended hereto.

We claim:

1. A composition of matter comprising a hydrocarbon, oil and a magnesium salt of a substituted oxy acid of phosphorus.

75 2. A composition of matter comprising a viscous hydrocarbon oil and a magnesium salt of an acid 01 the type formula:

wherein R and R are hydrocarbon radicals.

4. A composition of matter comprising a lubrieating oil and a magnesium salt of a substituted 6. A composition of matter comprising a hydrocarbon lubricating oil and a chromium salt of a substituted oxy acid of pentavalent phosphorus containing an alkaryl substituent and having more than twelve carbon atoms in the molecule.

'7. A composition of matter comprising a hydrocarbon lubricating oil and a magnesium salt of a substituted oxy acid of pentavalent phosphorus. containing an alkaryl substituent and having more than twelve carbon atoms in the molecule.

8. A composition of matter comprising a hydrocarbon lubricating oil and an aluminum salt of a substituted oxy acid of pentavalent phosphorus containing an alkaryl substituent and having more than twelve carbon atoms in the molecule.

9. A composition of matter comprising a hydrocarbon lubricating oil subject to deterioration at elevated temperatures, and from approximately 0.05% to approximately 2% by weight based on said oil of a metal salt of a substituted acid of phosphorus containing an organic substituent, the metal of said salt being selected from the class consisting of Groups II, III, IV and VI of Mendeleffs Periodic Table of the Elements, said salt being of a type capable of inhibiting deterioration of said lubricating oil.

10.'A composition of matter comprising ahydrocarbon lubricating oil subject to deterioration at elevated temperatures, and from approximately 0.05% to approximately 2% by weight based on said oil-of a polyvalent metal salt of a substituted acid of phosphorus containing an organic substituent, said salt being of a type capable of inhibiting deterioration of said lubricating oil.

11. A composition of matter comprising a hydrocarbon lubricating oil and a minor proportion of a chromium salt of a substituted acid of phosphorus containing an organic substituent, said chromium salt being present in an amount suflicieiot substantially to inhibit deterioration of said 0 12. A composition of matter comprising a hydrocarbon lubricating oil and a minor proportion of an aluminum salt of a substituted acid of phosphorus containing an organic substituent, said aluminum salt being presgnt 'in an amount suflicient substantially to inhibit deterioration of said 011.

13. A composition of matter comprising a hydrocarbon oil and a polyvalent metal salt of an oxy-acid of pentavalent phosphorus containing an alkyl substituent and having more than twelve carbon atoms in the molecule.

14. A composition of matter comprising a hydrocarbon oil and a chromium salt of an oxyacid of pentavalent phosphorus containing an alkyl substituent and having more than twelve carbon atoms in the molecule.

15. A composition of matter comprising a hydrocarbon oil and a chromium salt of a dibasic oxy-acid of pentavalent phosphorus containing a substituent of hydrocarbon structure.

16. A composition of matter comprising a hydrocarbon oil and a chromium salt of a dibasic alkyl substituted oxy-acid of pentavalent phosphorus.

17. A composition of matter comprising a hydrocarbon oil and a chromium salt of a dibasic cetyl substituted oxy-acid of pentavalent phosphorus.

18. A composition of matter comprising a hydrocarbon oil and a chromium salt of a monobasic oxy-acid of pentavalent phosphorus containing' substituents of hydrocarbon structure.

19. A composition of matter comprising a hydrocarbon oil and a chromium salt of a monobasic oxy-acid of pentavalent phosphorus containing a substituent of hydrocarbon structure.

20. A composition of matter comprising a hydrocarbon oil and a chromium salt of a'monobasic alkyl substituted oxy-acid oi pentavalent phosphorus.

21. A composition of matter comprising a hydrocarbon oil and a chromium salt of a monobasic cetyl substituted oxy-acid of pentavalent phosphorus.

22. A composition of matter comprising a hydrocarbon oil and an aluminum salt of an oxyacid of pentavalent phosphorus containing an phosphorus containing an organic substituent,

alkyl substituent and having more than twelve carbon atoms in the molecule.

23. A composition of matter comprising a hydrocarbon oil and an aluminum salt of a dibasic oxy-acid oi pentavalent phosphorus containing 5 a substituent of hydrocarbon structure.

24. A composition 01 matter comprising a hydrocarbon oil and an aluminum salt of a dibasic alkyl substituted oxy-acid'oi' pentavalent phosphorus. I 10 25. A composition or matter comprising a hy drocarbon oil and an aluminum salt 01 a dibasic cetyl substitutedoxy-acid of pentavalent phosphorus.

26. A composition of matter comprising a hy- 15 drocarbon oil and an aluminum salt of a monobasic oxy-acid or pentavalent phosphorus containing substituents otvhydrocarbon structure.

27. A composition of matter comprising a hydrocarbon oil and an aluminum salt of a monobasic oxy-acid o! pentavalent phosphorus containing a substituent of hydrocarbon structure.

28. A composition of matter comprising a hydrocarbon oil'and an aluminum salt of a monobasic alkyl substituted oxy-acid or pentavalent g5 phosphorus.

29. A composition 01' matter comprising a hydrocarbon oil and an aluminum salt of a monobasic cetyl substituted oxy-acid of pentavalent phosphorus.

30. A composition of matter comprising a hydrocarbon lubricating oil containing more than 0.05% by weight based on the oil of a polyvalent metal salt of a substituted acid of phosphorus containing an organic substituent.

81. An addition agent, capable of inhibiting piston ring sticking, ror lubricating oils, comprising a concentrated solution in mineral oil or a polyvaient metal salt of a substituted acid of .40 said solution being capable of dilution with mineral lubricating oil to form a-homog'eneous mixture containing from approximately 0.05% to 2% by weight of the polyvalent metal salt base on the total amount of lubricating oil.

BRUCE B. FARRINGTON. JAMES O. CLAYTON. JOHN T. RUTHERFORD.

Certificate of Correction Patent No. 2,228,659. Januarj 14, 1941.

BRUCE B. FARRINGTON ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 1, first column, line 3, after and insert the article a; page 3, first column, lines 14 to 43 inclusive, Table 1 should appear as shown below instead of as shown in the patent P|| were refluxed with 5 gal. ethyl ether for 24 hr. Cetylphosphoric acid solution decanted.

Monospermol phosphoric. 112 gms. solid sperm alcohols, gms. P10; and 400 gms. ethyl ether treated as above.

Mono-ootadecylphosphorlc.. gms. octadecenol and c. c.

benzene treated with 56.8 gms.

P0011. Product was hydrolyzed to give a free acidic hydrogen.

Mono-oleylphosphoric 107 gms. oleyl alcohol and 28.5 gms.

P205 were refluxed in ethyl ether for 24 hours. Mono-"sperrnenyl phosphor- 107 gms. llquld sperm alcohols and lo. 27 gms. P10 refluxed in ethyl ether for 24 hours.

Di elohexa lphosphorie..- 150 gms. cyclohexanol and 87 gms. Cy my P205 refluxed with 150 gms.

ethyl ether for 24 hr.

(Cetylphenyl) phosphoric- 688 gms. cetyl phenol and 316 gms.

P1105 refluxed with ethyl ether for 24 hours.

Di-(amylphenol) phosphoric.-- 100 gms. amyl phenol and 43 gms. 1 P10; heated to F. for 15 hr.

page 3, first column, lines 51 to 61, Table 2, and page 4, first column, lines 2 to 12, Table 2cont1nued, the first two columns of the heading to the table should appear as shown below instead of as shown in the patent i Engine tests Leuson Compound 1 Pop F 2? gig Cleanliness 881C and that the said Letters Patent should be read with this correction therein that the same may coniorm to the record of the case in the Patent Oflice.

Signed and sealed this 4th day of March, A. D. 1941,

l E l HEN RY VAN ARSDALE,

Acting Commissioner of Patents.