US2252674A - Lubrication - Google Patents

Description

can Au 12, 1941 PATENT OFFICE wmuoarron Carl F. Prutton, Cleveland Heights, Ohio, assignor to The Lubri-Zol Corporation, Clevelan Ohio, a corporation of Ohio No'Drawing.

Application March 23, 1938, Serial No. 197,734

9 Claims. (Cl.252-54) I This invention relates as indicated to lubrication, and more particularly to an improved composition of matter which may be employed as an addition agent to lubricating compositions generally, (1) for tht purpose of imparting thereto certain desirable characteristics such as (a) the ability to maintain lubrication under conditions of extreme pressure and (b) resistance to oxidation and the formation of sludge; and/or (2) the ability to impart (a) improved lubricating properties to lubricating compositions, while at the same time, (b) reducing the corrosive effect of the lubricant upon the bearings and associated metallic parts.

By extreme pressures" are meant pressures of" or substantially in excess of 10,000 lbs. per square inch, such pressures now being commonly encountered in hypoid gears, bearings, contact surfaces of cylinders and piston rings in internal combustion engines, and many other points. Such pressures between rubbing surfaces are beingencountered with increasing frequency as the arts progress.

It is, therefore, the principal object of my invention to provide an addition agent for lubricating compositions which will improve the lubricating properties of such compositions with respect to one or more of theabove-named desirable characteristics. Other objects of my invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, said invention, then, consists of the means hereinafter fully described, and particu-- larly pointed out inthe claims, the following description setting forth in detail certain approved combinations of ingredients embodying my invention, such disclosed means constituting, however, but certain of various forms in which the principle of the invention may be used.

Broadly stated, this invention comprises the provision of addition agents for use in lubricating compositions, which addition agents may be described as reaction products of complex organic oils, fats, or waxes. with a phosphorusand halogen-containing reagent.

In the foregoing definition of the generic invention there has been employed the term complex organic oils, fats, or waxes. By this term. as used in the specification and in the claims, is meant that general class of products of which the specific examples hereinafter given are representative.

Inasmuch as the addition agents provided by this invention for use in lubricating compositions may be very conveniently and correctly described by having reference to their mode of preparation, 1. e., the materials used in the reactions producing the addition agents, it is believed that the following classification of the reaction materials will describe the addition agents with suflici'ent accuracy.

The complex organic oils, fats and waxes which may be used in the preparation of addition agents contemplated by this invention may be classified as follows:

other method, as for example,

Alox. (Burwell pat.)

The phosphorusand halogen-containing reagents contemplated for use in my invention in providing theimproved addition agents may be classified from the standpoint of the desirability of the products produced thereby according to the valency of the phosphorus, viz:

I. Valency of phosphorus three or less:

Phosphorus chloride P2014 Phosphorus tpichloride; POI: Phosphorus tribromide PBrs Phosphorus tri-iodine PI: Phosphorous oxy-chloride POCI Phosphorous sulpho-chloride PSCI Halogen derivatives of phosphine and organic substituted phenyl chloride, (Cal-Ts) PO12 II. valency of phosphorus more than three:

Phosphorus pentachloride PCls Phosphorus dichlor-trifluo- PClzF:

ride Phosphorus trioxy-tetra- P203014 chloride Phosphorus oiwchloride POCla Phosphorus oxybromide POBra Phosphorus thiochloride PSCh Phosphorus thiobromide PSBrz Phosphorus thiobromide PaSsBn Phosphorus iodochloride P1201; Phosphenyl oxychloride (CoHs) OPClz f the improved addition agents provided by this invention, those formed from oils, fats, or waxes of mineral origin are usually to be preferred for the reason that the addition agents resulting therefrom are generally more resistant to oxidation and sludge-forming tendencies than those produced from oils, fats, or waxes of non-mineral origin.

The addition agents produced by reactions with reagents of the group in which the phosphorus has a valency of three or less are usually preferred for the reason that such addition agents, in general, produce desirable combinations of characteristics in the lubricant to which they are added in that the resulting lubricant is simultaneously particularly resistant to oxidation, as well as having a less corrosive eilect on metallic bearings and associated parts as compared with the untreated lubricant.

A preferred class of addition agents for use in phosphines, e. g. phoswhich oxidation or corrosion-inhibiting is of especial importance are reaction of oils or waxes a reagent in which the phosphorus has a valenc: of three or less for the reasons indicated above As a specific example of this last class of preferred addition agents, the following may be mentioned:

The product produced by reacting a reflnec' mineral lubricating oil, preferably of Pennsylvania origin with phosphorus trichloride.

The procedure in producing such product is as follows:

In general, the reaction is carried out by adding to the complex organic oil, fat, or wax, hereinafter for convenience referred to as a complex oil, a minor proportion of the phosphorus and halogen-containing reagent. The exact proportion of the reagent will depend upon the nature of the oil and the reagent, in most cases being on the order of 5 to 30% by weight and preferably of a sufficient amount so that an excess will be present, as indicated by the presence of untreated reagent at the end of the reaction those produced by th of mineral origin witl period.

The mixture is heated to a temperature of about C., the exact temperature depending upon the boiling point of the reacting materials which, in the case of volatile materials, may make it necessary to heat under pressure. In most cases, atmospheric pressure may be employed and the reaction vessel provided with a reflux condenser to prevent loss of the reacting materials during the heating period.

In the case of certain of the less reactive :reagents higher temperatures may be required to cause the desired reaction, for example, as high as C. or even 200 C. or more.

may be preferred to carry out the reaction in the vapor phase as, for example, by volatllizing the materials to be reacted and passing the mixed vapors through heated tubes or causing reaction to take place by means of other types of equipment or methods of promoting reaction.

The reaction period is preferably continued for about 1 to 10 hours; in most cases, three hours being a suilicient length of time. At the end of the reaction period, the product may be washed with water to decompose and remove the excess reagent, or it may be desirable to wash with solutions of alkalies or to treat with solid alkaline materials, especially where the reagent is of a more stable type.

After removal of the excess reagent, it is usually desirable to remove from the material such unstable or easily decomposed products as are still present. This may advantageously be done by blowing with steam, or treating with solutions of alkalies, or by heating with solid alkaliar: materials to a temperature of from 100 to The following example is given by way of illustration, only:

A Penna. bright stock is treated with about 20% by weight of phosphorus trichloride PCla, the mixture heated to boiling in a glass, or glasslined, vessel provided with a reflux condenser, for about three hours. The product is washed with water and then blown with steam for about 1 one-half hour and finally diluted with benzene to facilitate separation from the water layer; the benzene layer is then separated and the bellzene removed by distillation, leaving the final product-as the residue. The appearance and physical characteristics of the product thus obtained are quite similar to that of the original bright stock. An analysis showed a chlorine content in-the product of about 0.7%.

Another addition agent was prepared in. exactly the same manner as above described using planation, it is believed that the workers in the art will be able to determine very readily the particular concentrations which produce the 1% of the addition agent produced, as previously explained, from Penna. bright stock or neutral oil, caused a very marked reduction in the corrosion of cadmium silver and lead bronze bear- 5 ings exposed to a Penna. S. A. E. motor oil a Penna. neutral oil instead of a Penna. bright for a period of 192 hours at a temperature of stock and the two resultant products were sub- 150 C. stantially equivalent in their physical charaoter- While it is believed that the film strength imistics and general effectiveness as addition proving eflect of the addition agents of this ina ts- 10 vention may be due to a chemical or P 37 100- Other addition agents were prepared by treatchemical action upon the metallic surface under ing the following in a similar way with phosconditions of extreme pressure, it is to be unphorus trichloride: dertsood that this invention is not intended to be limited by any explanation or theory. The 8133 222 2 2322 35 15 corrosion-inhibiting effect may be obtained ei- Furfuml extract of mineral oil ther by protective action on the metal surfaces u gas on or a catalytic effect of the phosphorus in the composition, or the addition agent may react The addition agents contemplated for use in with the oil to render it relatively non-corrosive. this invention may be added to any conventional The precise action is not known. lubricating oil, such as mineral 011 (more spe- The following tables give the results of cerciflcally, motor oils), and may be employed in tain corrosion tests on diil'erent bearing alloys various combined oils so long as the remaining by the base oil and the same oil to which has constituents are not incompatible with the adbeen added different addition agents prepared dition-agents herein defined. The concentration as above explained.

of addition agents found most useful in mineral lubricating oils will vary, for example, becon-0mm test 192 hours at tween about of 1% up to 2%; however, higher 011 Percent change in concentrations up to 20% may be employed for weight particular uses. gg g gf The presence of the named addition agents Type S.A.-E 53; Lead Babin substantial proportions in lubricating comsilver hm positions generally, will usually improve certain properties such as the extreme pressure char- 10 None -o. 12 0. 51 0.00 acteristics of the composition, even though the flagg3 addition agent may be present over a wide range I 1 Neut.-PCl3.:: I of concentrations. Corrosion tests on lubricants i E igggqg containing various concentrations of certain of Pennsylvania the addition agents have shown, however, that 4 g ggggjggg for certain types ofoil a low concentration, 40 413i. St.-PCl;

i. e., on the order of one-half percent or less, e i if gif;

will markedly improve the corrosion character- Non e istics of the lubricant; whereas, concentrations M16430; figggigggfi of 1% effect no improvement and may, in innent. 30 -%Br.-St.PC1-

stances, increase the corrosiveness of the com- 23111:: i if'fi jj gjj position. In the case of other addition agents or other base oils concentrations of may It will be noted from the above table that have no marked influence on the corrosion facwhen the correct percentages of addition agent tor; whereas, concentrations of 1% have been are employed, the loss of weight of the bearings found to materially improve the corrosive tendis as little or even less than when the untreated encies of the oil. In determining the concentraoils are used.

tlons which will produce the best results, tests The following table indicates the results of may advantageously be conducted with the parcertain well-known tests designed to show the ticular base oil to which the addition agents are condition of the oils at intervals during their to be added; however, with the foregoing exuse. It will be seen therefrom that the oils to which the addition agent has been added show marked improvements over the ordinary lubricating oils and a general resistance to deteriorabest results. For-example, I have found that tion. Indiana oxidation tests Type Penrn- PenrL-- Penn --{%A.E Non t 610811 0H8- Inhlblt" Agent Noneut-P015-.. at. strata- Oonradson Original"--- 0.18.-- 0.14 0.18

car n. hours-. 1.78.-. 0.89 0.77 Viscoslty 0riginal 46.3.-- 47.0 46.9.-

100 hours-.-- 52.9--. 43.3 4.8.9 Percent in- 14.2-.- 3.8 4.2 S.U.S.at210 crease in F. viscosity at 100 H hours. 1

OIIIS 1'6- quimq 1 10 mgs 32.5... 87.0 82.5 M rg than M o ra than 1 5 than gg g 100mgs 96.0-.- Morethanlfifl. Morethanl50.

'Neut.-PCI;=Pennsylvanla -neu treated with phosphorus trichloride.

.Br. St.-POh=Pennsylvania bright stock treated with phosphorus trichloride.

"Indiana oxidation tests T Mid-continent Mid-continent Mid-continent Mid-continent. OiL ?1%No- $1110 2 30 so.

- ercen one l Agent None. Neut.-Pl; n St.-PC1.1 B2". Sit-PO13. Oonradson {O 0 0. 0.49.-. 0.47.

carhpn. 100 urs 2 1.26. Viseosrty---.. 0r 63.7. 100 ours--- 68.7. S. at Percent in- 7.8.

0 F. crease in viscosity atl00hours. Hours re quired for mgs 39.5.. 07.0.- 76.0 Approx. 170. pizeclfpital00mgs 97.0 145.0.-. 760.... Approx. 170.

Nore.-Test was continued until amount of precipitate was at less in 150 hours or less. Otherwise test was discontinued at 150 hours.

The following is a description of an example illustrating the type of lubricating composition included in the present invention.

Fifty-five pounds of Pennsylvania Bright Stock were placed in an' iron reactor equipped with a suitable heating device, agitator, cover, and reflux condenser. chloride were added and heated to 180 C., and maintained at that temperature for about 1% hours. The contents of the reactor were then cooled, transferred to a wooden tank, and diluted with about 7 gallons of benzol. About 7 gallons of water were placed in the same tank and the two layers thoroughly agitated together. The water was then allowed to settle and the water layer drawn off from the bottom of the tank. The water wash operation was repeated, and 1% hours allowed for separation of the water layer before removing.

Low pressure steam was blown through the remaining product for two hours, after which the product was allowed to stand for about 48 hours to efi'ect complete separation of the entrained water.

The benzol solution was then transferred to a glass-lined vacuum still and the benzol removed by distillation under a vacuum equivalent to 27" of mercury. The distillation was discontinued when the temperature of'the liquid in the still reached 110 C.

The product thus obtained had the following characteristics:

Per cent free HC] 0 Per cent ash .10 Per cent chlorine 1 .023 Per cent phosphorus .046 Vis. at 210 F. in S. U. S 148 product was.found tmbe a very effective oxidation inhibitor when incorporated, in an amount of about 1% or less. in various types of mineral lubricating oil. The oxidation inhibiting effect of this product was tested by means of a modified Indiana oxidation test in which the conditions were, in general, the same as those previously described for the Indiana oxidation test, with the exception that a coil consisting of 9 feet of 18 gauge iron wire, polished with emery cloth, was placed in the oxidation tube entirely submerged in the oil sample.

The results obtained with this test on three different types of oil, and the same oils containing 1% of the product prepared according to the above description, are shown in the following table:

1.1 pounds of phosphorus tri-.

t 100 mg. in case this amount was precipitated Pennsylvania Pennsylvania Mid-continent SAE 10 SAE 40 SAE 30 motor oil motor oil motor oil No +1% No .5% No .s% addiinhibaddiinhibaddiinhibtlon itor tion itor tion itor CONTINENTAL OXIDATION Conradson carbon:

Original..... .19 .15 1.30 1.01 .34 .11 At 48 hours. 3. 05 75 2. 58 l. 49 2. 32 l. 26 Saybolt vis. at

Original" 46. 5 46. 7 82. 9 83. 9 63. 5 64. 0 All 48 hours. 64. 8 48. 6 93. 9 86. 6 81.5 72. 4 Percent vis. inc. at 48 hours 39.3 4.0 13. 05 3. 0 28. 4 13.0 Naphtha insol.

Hrs. for 10 22.5 42.0 14.5 33.0 Hrs. for 100 mgs 40.5 32.5 Mgs. at 48 hrs 217. 0 14. 8 4.0 8. 2 210 44. 9 Acid number 01'iginal .17 .08 .04 .11 .08 At 48 hours. 2. 23 .81 1. 26 37 1.38 73 SHELL CORROSION Percent change in weight:

Lead-bronze. 1. .07 l0 10 15 l0 Babbitt-.. 18 .05 0 .0l 0 04 Other modes of applying the principle of my invention. may be employed instead of the one explained, change being made as regards the materials employed in carrying out the process provided the ingredient or ingredients stated in any of the following claims or the equivalent of such stated ingredient or ingredients be employed.

I, therefore, particularly point out and distinctly claim as my invention:

1. A lubricating composition comprising a mineral lubricating oil with the properties of such composition affecting its use as a, lubricant improved by incorporating therein from an effective amount to about 20%, based on the amount of mineral oil, of a composition selected from the following class;-the reaction product of a complex organic wax of mineral origin and a phosphorus-and-halogen-containing reagent in which the phosphorus has a valence of three or less; the reaction product of a complex organic oil of mineral origin and a phosphorusand-halogen-containing reagent in which the phosphorus has a valence of three or less; the total amount of phosphorus in the lubricating composition being less than {6% thereof.

2. An addition agent for lubricating compositions, comprising the reaction product of complex organic oil oi mineral origin with a phosphorus-and-halogen-containing reagent in which the phosphorus has a valence of three or less, such product containing less than 6% of phosphorus.

3. An addition agent for lubricating compositions comprising the reaction product of a complex organic wax of mineral origin with a phosphorus-and-halogen-containing reagent in which the phosphorus has a valence of three or less, such. reaction product containing less than 1 6% phosphorus.

4. A lubricating composition comprising a mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein from an eflective amount to about 20%, based on the amount of mineral oil, of the reaction product of a complex organic oil of mineral origin and a phosphorus-ancl-halogen-containing reagent in which the phosphorus has a valence of three or less,

said reaction product containing less than {6%- phosphorus.

5. A lubricating composition comprising a mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein from an effective amount to about 20%, based on the amount oi mineral oil, of the reaction product of a complex organic wax of mineral origin and a phosphorus-and-halogen-containing reagent in which the phosphorus has a; valence of three or less. said reaction product containing less than 155% phosphorus.

6. A lubricating composition comprising a mineral lubricating oil with the properties of such composition aiIectinB its use as a lubricant improved by incorporating therein from about 0.1% to about 2%. based on the amount 01 mineral oil, or the reaction product or a complex organic oil of mineral origin and a phosphorusand-halogen-containing reagent in which the phosphorus has a valence of three or less, said reaction product containing less than 1 6% phosphorus. r

'1. An addition agent for lubricating compositions comprising the reaction product of a complex organic oil of mineral origin with a phosphorus-and-chlorine-containing reagent in which the phosphorus has a valence of three or less. the total phosphorus content of suchreaction product being less than 8. An addition agent for lubricating compositions comprising the reaction product of mineral oil with a phosphorus-and-halogen-containing reagent in which the phosphorus has a valence of three or less, said reaction product having a phosphorus content of less than .05%

9. A lubricating composition comprising a mineral lubricating oil with the ability of such composition to resist oxidation improved by incorporatingtherein a small amount. based on the amount of mineral oil, of the reaction product 01 a complex organic oil of mineral origin with a phosphorus-and-chlorine-containing reagent in which the phosphorus has a valence or three or less, said reaction product containin less than about .05% phosphorus.

CARL F. PRUTI'ON.