US2655477A - Mineral lubricating oil containing an anticorrosive agent and an antioxidant detergent agent - Google Patents

Description

Patented Oct. 13, 1953 MINERAL LUBRICATING OIL CONTAINING AN ANTICORROSIVE AGENT AND AN ANTI- XIDANT DETERGENT AGENT John D. Bartleson, Cleveland, and Milton H. Campbell, Cleveland Heights, Ohio, assignors a. corporation of Ohio No Drawing. Application December 27, 1948, erial No. 718,890

1 Claim. (Cl. 252-323) This invention relates to lubricants, and more effects or the agents on each other, as well as on particularly to lubricating oils containing both the oil, will be increased manifold times.

internal combustion engine operating at high lacquer which protects the metal parts. Thus it are involved in attaining a single lubricating oil on the pist ns due to the pr s e f e anticorrosion additive, would also remove the protective film on the bearings, thus obviating the beneficial elfect of the corrosion inhibitor. Such has been the case with many anti-corrosion in contact, as well as low oxidative deterioration, additives- For instance. a Small am n of p,p-di-(dimethylamine)-diphenylmethane satisthe reaction product of dioctadecylamine with Another approach to the problem of producfi- However, in so doing. i w r he p n ing a lubricating oil which shows little or no lacquer deposition and little or no corrosion of lubricant comes in contact, as well as little or no 18 W0 r m i i agents from th h ragent imparting at least one of the desired char.- acteristics, viz.: anti-lacquer, anti-corrosion, tp q t, t th 11 I t approagh t a phosphorus sulfide with a lower olefin having effect or the addition agents upon each other this characteristic. For in t n many t 40 as to lacquer and sludge characteristics. The

quer or detergent type agent may be added to gi i gi z gzi?f i igz zgiig izg gggii g g a lubricating oil composition together with the above described anti-deterioration agent and the resulting blend will have substantially the des'r bl -1 er 0 also not interfere with the anti-lacquer efl'ect of I a e non acqu mg haractenstlcs imparted by the detergent-type agent plus substantially the th fi agent if the lubricant is to have desirable anti-deterioration characteristics imistics, it is evident that these factors or interanti-lacquer agent are overcome by the anti-corfrom the desirable anti-lacquer characteristic imparted to the oil by the detergent-type agent, and

likewise the detergent-type agent-does not detract from the desirable anti-corrosion: characteristic imparted by the phosphorus 'sulfide-olefinagent. This discovery is of especial commercial significance in view of the relativelylow cost of the cent is especially desirable. Even small amounts show a significant improvement, and economic factors would make it undesirable to use more than is necessaryito achievethe desired improvement.

Phosphor pentasulfide is prepared although other phosphorus sulfides or mixtures of sulfides may, be. employed Phosphorus pentasulfide is mosteconomicand readily available and for this rea e ts used i'n the illustrative examples. Un-

der suitable cond itions sulfides of arsenic or anphosphorus sulfide-olefin typeagent andsome of H EBB-carbon atomsin the molecule are preferred. A

the more efficient metaltype'anti lacquering agents (which are very corrosive, however), as

well as the ease with which thebl'endsmay be. pre-,

pared.

The objects achieved in accordance with the invention include the provision of a blend of agents which blend may be useful itself as a lubricant an r d which when blended-inlubri'cating oils Will -markedly improve the lacquer sludge,

corrosion and other characteristics thereof; the

provision of relati'vely non-lacquering and nondeteriorative lubricating oils containing such agents; and other objects which will be apparent as details or embodiments of'the invention are set forth hereinafter.

The detergent type agents Thedetergent-type agents which may be used contain one cr-more of an alkali metal, suchas sodium, potassium. and lithium, oran alkaline earth metal, such as calcium, barium and strontium. They may be illustrated by an. alkalior alkaline earth-metal'derivative ofa reaction product of phosphorus pentasulfide withan amine, such as dioctadecylamineor octadecenylamine. These neutralized phosphorus pentasulfide de-. rived agents impart certain anti-oxidant characteristicstothe blend, also. They impart to the oil the uncles able characteristic of corroding metals, especially the bearing metals with which the lubricant contacts. 7

- The amount of the detergent type agent usually added to the oil or grease dependsupon the characteristics of the :oil or grease and the intended use, askno-wnto the art, and in generalranges from afractionofone percent'up to about ten percent.

The anti-deterioration agent The anti-deterioration agent employed in accordancewith the invention i a phosphorus sultide-olefin reaction product-which may be made with direct admixture of the reactants, or, if desired,- by their admixture inthe presence of a diluent which may or may not be subsequently removed. A heavy oil such as white oil, or a lubricating oilhaving about the same properties as that to which the new composition is to be added may be used as a diluent. The reaction is usually completein about 10 hours or less time. The reaction time isa functionof the temperature, the amount ofthe sulfide that isto react, the subdivision of the reactants, the rate of stirring,

etc;

The olefin or mixture of olefin may be reacted with the phosphorus sulfide or a mixture of phosphorus sulfide in weight ratios from 5 to about 95 weight per cent of the phosphorus sulfide based on the weight of the olefin, depending on the mo,- lecular weight of a the olefins used. Generally about 25 to about '75 per cent is the usual range that will be used, and about 50 to about70 per i "In ee er tim'onymay-be-s ilarly employed.

1, ol efins having from about 6 to about Motor by non-selective polymerization, e. g., with a 'plio'sphorus acid type catalyst. A polymer gasoline fraction may be removed therefrom byfractional distillationto the 250F$cut point, and the residue is known as reducedmotor-polymer." The reduced-motor polymer maycontainsmall amounts of materialslighter than the trimer. Its average molecular weight 18 aboutand' it preferably containsqar major amount of olefins boilingbelowSOOF. The olefins usedshouldbe 'of asufficientlyhigh molecular weight to give-a final-product having-the desired 0' dispersibility.

The reactionmay be carried out-in the presence or absence-oi air, or in an atmosphere of inert or non-deleterious gas, suchas nitrogenor H28. It may also be carried out under pressure, e. g:, thepressure generated whenthereaction is carried outin-a closed vessel.

The yield isvery high and appreciable amounts of; oilinsoluble products are not formed. Gen+ erally' the amount of sulfide ischosen so .thatall of it will react at the temperature selected and thereactionis continued until it is consumed.

After the reaction is complete, the sulfide-olefin reaction product is-suitable foruse as, an anti-. corrosion addition .agen but preferably it is first processed, for instancacentrifuged or filtered; to remove water and any traces of oil-insolublebyproduct substances-f.

The amount. of the Isulfidesolefin tobe incorporateddn the-.toilorgrease, together with'the anti-licquer detergent typeagent, will;also.,de+ pend upon theintendeduse.aswellas the :characteristics of the oil or grease, andinygeneral, amounts inthexange f from 0.92 percentto 2-.0 per cent by. weight, based on thecil, are suitable. Even small amounts show a significant improvement and it is uneconomical to add more than isnecessary to impart to the lubric'antthe desired properties. v

The following examples or tests of lubricant compositions, prepared accordance with the invention, will serve to] illustrate and point out someadvantages but in-no wise to limit thescope "of the invention as otherwise disclosedand claimed herein,

Anti-corrosion addition agent 2655,47! g 6 EXAMPLE 2 nlsh, sludge and overall rating of'the blends AnfiJacquer addition agent containing the two agents, in accordance with he invention. Furthermore, the viscosity in- The barium derivative of the reaction product crease rating is improved somewhat, and t of phosphorus pentasulfide with dioctadecylamine was prepared in accordance with known probjnat1'0nb1ends cedures by reacting phosphorus pentasulfide The piston skirt rating remained high throughwith the amine and then treating the reac i out the test of the blend containing 0.38 per cent product with barium hydroxide octahyd ate (S of the anti-corrosion agent (column 5) and was U- S. Paten N 4)- This s t 9.5 after the test was extended to 72 hours. Even d ti n a ent of E ampl 2 us d in t t sts after the 72-hour test the oil was substantially ferred to hereinafter, in conjun on Wi h the unoxidized, as indicated by testing the used oil. sulfide-olefin anti-corrosion blending a en This is remarkable in view of the high anti- In testing the oils containing the addition lacquer characteristics and low corrosion chara ents the so-called standardized '"Chevr acteristics of the lubricant blend prepared in Engine Test was used. In this test, new piston accordance with th i e t n, rin s an w n w copper-lead bearing inserts The blend made in accordance with the in are installed in the motor prior to each test. vention was also tested by the Caterpillar 96- The engine is a conventional Chevrolet engine hour single-cylinder 4-cycle diesel engine test With 216-5 cupiston displacement a which was developed several years ago as ashortmp o ratio o 6- t0 The e i is ened version of the standard 480-hour Caterpillar Operated at 3150 With a l a of 30 l-A test (CRC-L-l). .It is of considerable valuein B. H. P. and at a temperature at the jacket o predicting the performance of an oil in the let of 200 F. The lubricating oil temperature standard test, although it is somewhat more is maintained at 265 F. for an SAE 10 grade oil, severe t t tt The purpose of the and at 280 F. for oils of SAE to 50 gredeshour test is to determine the elTect of lubricating The fuel used contains from 2 5 to 3 0 ml tetraoils on ring sticking, wear, and the accumulayl lead per ga n Bes des th Welght 105$ tion of deposits in a single cylinder 4-cycle diesel of the test bear n s, d p t In the power engine having a standard crankcase designed tion, and p operties of the used oil, a p 30 with minimum "recesses .or pockets to retain oil, near the middle and also at the end of the test, a cylinder bore of 5.75 in., .a stroke of 8 in..and

are examined. a piston displacement of 208 cu. in. The engme A conventional solvent extracted lubricatin is operated at about 1000 R P M under a load oil base stock (SAE 30) and blended compos1- o 19 B, for a fuel input of b t 3000 tions of this oil made in accordance with the t per minute for 96 hours (continuously, if invention we e Submitted 110 36410111 tests in possible), with an inlet cooling jacket temperaaccordance with the above Chevrolet engine proture of about 135 E and an ut t temperature cedure. The results in the following table are of about 5 The temperature of t oil yp going to the bearings is about .195 F., the air TABLE I inlet temperature is about 95 F. and the oil pressure at the bearings is 30 p. s. i. At the end Column No 1 2 v 4 5 of the 96-hour test the liner, piston, rings, crank- Conccntration of Example} (anti-corrosion) agent in percent by weight Concentration of Example 2 ifii gt tgfgti f m to 2 o and after the test. The maximum wear is re- Piston skirt rating. r corded as the difierence between the initial and Varnish rating i- 48. 75 43.00 .0 49. 49. 25

Sludgerating .2 gs g final readings The maximum and minimum top Overallrating Corrosion of CwPh bean-mg 50 ring side clearance is observed both before and gletal (l'filfiglllllsilwt. loss per 1 8 169 after the test and is recorded The oil filter sfilty mtris?::::::::::: 210 136 162 1a l ment is ompletely inspected at the end or Pentane insolubles (mgms.) 110 184 Column 3 shows that the anti-lacquer agent 55 cal rating system similar to the Navy has excellent piston skirt p -f sludge and Dartment Demeritsystem. The individual enoverall ratings, but the corrosion is bad. One

would expect these excellent ratings to be brought down by the addition to the anti-lacquer g i g i gg g gfi g figg g ggfgfi z ig; 8O inspection of conditions chargeable to the-lubripiston skirt, varnish, sludge .and overall ratings cant 1391991115 for h item then ll t d for th i tt t, by weighting factors which closely establish the col n 4 and ol n 5 or th bov t bl relative importance of the engine factors inhowever, show that in blends containing the g5 volved. 'The weighted demerits are totalled and anti-lacquer agent and also the anti-corrosion subtracted from 100fort'he finalor merit rating.

varnish rating is even slightly better than that A. En ne c eanliness of the blend contalnm'g the anti-lacquer agent alone (column 3). The sludge rating and over- 7 all rating are substantially e uivalent to those l r of the oil blend containing on y'the anti-lacquer engme parts" hsted the following agent (column 3 T great improvement in tions, are evaluated between the demerit range the corrosion characteristics is particularly note- 01730, f el' n n ne n rt, rend J10. the maximum worthy, especially in viewer the excellent 'vardepositions. ThG'FGIEfiWJMIJOFtBIIGEvDf =deposits in regard to engine. performanceis reflected by the weighting factor involved;

Possible weighted demerits 1. Ring sticking 2 2. Liner deposits (cylinder above ring trave 1 0 3. Cros 1.5

4. Heat groove deposit (top laud) 5. Ring groove deposits 6. Piston land deposits 7. Oil system sludge deposits.

Total possible weighted demerits 100 The rating of this item is notpossible when standard L-l 480-131. piston (EX7288) is employed. Therefore, the total weighted demerits is divided by 90 to convert the final rating to a 100 basis when this item is not included in the rating.

13. Overall wear The initial ratings are made in accordance with a demerit system. When no measurable wear of the piston rings and liner or sending of the piston is evidenced, the demerit value is scored as 0. When the assigned limits of wear and scuffing (itemized below) are exceeded, the demerit value becomes 10. Intermediate values are judged accordingly. The final rating is computed from the following three factors which are adjusted by weighting factors in accordance with their relative importance in the test:

Possible Weight- Possible basic in weighted demerits factor demerits i 1. Cylinder liner wear 4. 0 40 2. Compression ring wear 10 2.0 20 3. Piston scufilng (above rop ring) l0 4. 0 4() Total possible weighted de merits"... 100

A blend of conventional solvent extracted Mid- Continent lubricating oil base stock (SAE 30) containing 0.38% by weight of the anti-corrosion agent of Example 1, and 1.5% by weight of the anti-lacquer agent of Example 2, based on the oil, was tested in accordance with the above Caterpillar 96-hour procedure and the following esults were obtained.

Possible Actual demerits demerits Ring sticking 20 0 Liner deposits.. 10 2. 9 Skirt deposit. i5 .2 Heat groove depos l0 .7 Ring groove deposit 20 1.2 Piston land deposits 20 8 Oil system sludge 5 .'05 Total demerits 100 5. 85 5/ Cylinder linear wear 40 2.0 Compression ring wear 20 2. 6 Piston scuffing 40 12 Total 100 16. (i

It is evident from the foregoing table that the oil blend made in accordance with the invention shows a very high merit rating.

The Sohio corrosion test was used in evaluating other blends made in accordance with the invention. This test is described in U. S. Patent No. 2,464,233, dated March 15, 1949, to E. C. Hughes, J. D. Bartleson, M. L. Sunday and M. M. Fink, which also correlates the results of the laboratory tests with a Chevrolet engine test. :Essentially the laboratory test. equipment consists of a vertical thermostatically heated glass test tube mm. outside diameter and 42 cm. long) into which is placed the corrosion test unit. An air inlet is provided for admitting air into the lower end of the corrosion unit in such a way that in rising the air will cause the'oil and suspended material therein to circulate into the corrosion unit. The tube is filled with an amount of the oil to be tested which is at least sufficient to submerge the metals being tested. The corrosion test unit essentially consists in a circular relatively fine grained copper-lead test piece of l%- O. D., which has a diam eter hole in its center (i. e. shaped like an ordinary washer). The test piece has an exposed copper-lead surface of 3.00 sq. cm. Of this surface area, 1.85 sq. cm. acts as a loaded bearing, and is contacted by a part of the cylindrical surface of a hardened steel drill rod diameter fi long, and of 51-57 Rockwell hardness).

The drill rod is held in a special holder, and the holder is rotated that the surface of the drill rod which contacts the bearing sweeps the bearing surface (the drill rod is not rotated on its own axis and the surface of the drill rod which contacts the bearing is not changed).

The corrosion test unit means for holding the bearing and the drill rod is a steel tubing (15" long and 1 O. D.) which is attached to a support. A steel cup (1" longyl e O. D. by I. D.) is threaded into the steel tube, at the lower end. The cup has a diameter hole in the bottom for admitting the oil into the corrosion chamber. The copper-lead test piece fits snugly into the steel cup and the hole in the test piece fits over the hole in the steel cup. A section of steel rod in diameter and 19" long) serves as a shaft and is positioned by 2 bearings which are fixedly set in the outer steel tubing, one near the top and one near the lower (threaded) end thereof. Several holes are drilled just above and just below the lower hearing. The holes above the bearing facilitate cleaning the apparatus, while the holes below the bear: ing enable the circulation of oil through the corrosion chamber. The drill rod holder is connected to the shaft by a self-aligning yoke and pin coupling. This assures instantaneous and continuous alignment of the drill rod bearing member against the bearing surface at all times. A pulley is fitted to the top of the steel shaft and the shaft is connected therethrough to a power source. The shaft is rotated at about 675 R. P. M.; and the weight of the shaft and attached members is about 600 grams, which is the gravitational force which represents the thrust on the bearing. inlet pumps the oil through the chamber containing the test piece and out through the holes in the steel tubing.

The ratios of surface active metals to the volume of oil in an internal combustion test engine are nearly quantitatively duplicated in the test equipment. The temperature used is approximately that of the bearing surface. The rate of air flow per volume of oil is adjusted to the same as the average for a test engine in 011- eration. of the catalytic effects, those due to soluble iron are the most important. They are empirically duplicated by the addition of a soluble iron salt. Those due to lead-bromide are duplicated by its addition.

The test was correlated with a slightly modified version of the L-4 Chevrolet test. This modification comprised reducing the oil additions from the 4 quarts in the usual procedure 2 quarts, by reducing the usual 1 pint oil additions which are pint additions.

made at 4 hour intervals to This modification increases the border line oils.

For each test, the glass parts the usual chromic acid method, rinsed and dried.

A new copper-lead test piece is used for every tes The test piece is polished before use, on a surface grinder to give it a smooth finish.

before and after the of the test is begun.

The laboratory test conditions which were found to correlate with the modified Chevrolet procedure 36-hour test are shown in the following table.

TABLEA Temperature 325 F. il sample 107 cc. Air flow rate 70 liters/hour. Time hours. Catalysts Steel.

EXAMPLE 3 The potassium derivative of the reaction product of phosphorus pentasulfide with an unsaturated amine A commercially available unsaturated primary amine mi tu e on a ni g about 80 per cent by F. for three hours. blown with TABLE II Column No 1 2 3 Anti-corrosion agent of Example 1 con cfintration in percent by weight (of o None None 0.38 Anti-lacquer agent of example No None 3 Concentration of anti-lacquer agent in percent by weight (of oil) None 1 1 Colgosion of Ou-Pb (in mgms. wt. loss 0 -i 5 Viscosity increase (S US) 18 cut. N o 4 rived metal type improved as to anti-corrosion and anti-oxidant characteristics by the incorporation of a sulfideolefin anti-deterioration agent, in accordance with the invention, without impairing the antisludge characteristics imparted by the metal type agent.

We claim: A mineral oil lubricant comprising a major product of phosphorus pentasulfide and reduced motor polymer in the ratio of about 1.5 moles reduced motor polymer per mole of phosphorus pentasulfide, formed at about 350 F. for about 12 eight hours, and said. antioxidant detergent agent References Cited in the file of this patent;

being an oil-dispersible barmm derivative Q1 a JUNITED STATES EATENTS reaction product of phosphorus pentasulfide and dioctadecylamine m theratio of about 1.6 moles Number Name Date dioctadecylamineper mole of phosphorus penta- 5 23161078 Loam 6t 1943 su1fide,'-formed'at-about 500* F. 'for'a'bout thirty 251-61079 maneret Apr- 61 1943 minutes 2, .16,-080 Loans et' a1. Apr, 6, 1943 2,381,907 Hughes q Aug, 14, 1945 JOHN D -VBARTLES0N 2 4033194 Bartleson July 9, 1946 2347,60? .Zimmer -Aug. 24, 1948 MILTON-.11. CAMPBEIL- 10