US3801506A

US3801506A - Water-resistant greases

Info

Publication number: US3801506A
Application number: US00161993A
Authority: US
Inventors: E Cross; G Bright
Original assignee: Texaco Inc
Current assignee: Texaco Inc
Priority date: 1971-07-12
Filing date: 1971-07-12
Publication date: 1974-04-02
Anticipated expiration: 1991-04-02
Also published as: PH11908A; TR18719A; BR7204588D0; CA1000261A; NL7208877A; BE786090A; IT962684B; FR2145563B3; ES404606A1; GB1376835A; AU4384472A; DE2229065A1; FR2145563A1; AU456771B2

Abstract

THIS INVENTION CONCERNS THE USE OF POLYALKOXYLATED ALKYLATED PHENOLS AND POLYALKOXYLATED ALKYLENE DIAMINES AS ADDITIVES TO ENHANCE THE WATER-RESISTANCE OF GREASES THICKENED WITH LITHIUM SOAPS OR MIXTURES OF LITHIUM SOAPS AND CALCIUM SOAPS.

Description

United States Patent O 3,801,506 WATER-RESISTANT GREASES Edward A. Cross, Houston, and Gordon S. Bright, Nederland, Tex., assignors to Texaco Inc., New York, N.Y. No Drawing. Filed July 12, .1971, Ser. No. 161,993 Int. Cl. C10rn 5/16, 5/20 US. Cl. 252-40 9 Claims ABSTRACT OF THE DISCLOSURE This invention concerns the use of polyalkoxylated alkylated phenols and polyalkoxylated alkylene diamines as additives to enhance the water-resistance of greases thickened with lithium soaps or mixtures of lithium soaps and calcium soaps.

BACKGROUND OF THE INVENTION The prolonged contact of greases containing hydro philic components with an aqueous environment is usually detrimental to the grease. The reason for this is that hydrophilic components are attached by water, especially at elevated temperatures. When the hydrophilic agent is the gelling agent such as a lithium or sodium soap, attack by water is particularly acute because these soaps are emulsifying agents and tend to leach out. As a result of this extraction or leaching that alkali metal soaps undergo, the structure of the grease is degraded and, because of deficient lubrication, the part to be protected can be damaged or can fail.

Another area of concern caused by the poor resistance of greases to the attack of water is in the field of water pollution. For example, facilities such as foundries or steel mills which utilize large amounts of lubricants in processes requiring the use of large quantities of water for cooling or washing, frequently discharge hugh quantities of soaps or other grease components into the waterways which cause undesirable changes in the life cycle and appearance of the waterways. While it is sometimes possible to remove the grease pollutants from the waterways, it almost always is costly and can be avoided by use of prophylactic methods; in this instance, utilizing greases possessing good water-resistance. Unfortunately, up to this time little or no headway has been made in the formulation of relatively inexpensive greases which have good resistance to water attack.

In view of the problems caused by the use of greases having poor resistance to water in an aqueous environment, it is an object of this invention to provide additives of varying structures to impart substantially improved water-resistance to alkali metal soap-thickened, particularly lithium soap and lithium-calcium soap-thickened greases without adversely affecting the desirable characteristics of the grease.

Another object of this invention is to provide alkali metal soap-thickened greases which are substantially more recalcitrant to the attack by water than are comparable greases of the prior art.

Other objects will suggest themselves to those skilled in the lubrication art after a perusal of this disclosure.

DETAILED DESCRIPTION OF THE INVENTION by weight of mineral oil'of lubricating viscosity,

3,801,506 Patented Apr. 2, 1974 (b) From about 15 to 2 parts by weight of lithium soap or lithium-calcium soap, then adding to the preformed grease at about 180 F. to 200 F. with stirring:

(c) From about 0.1 to 5.0 parts by weight of at least one additive imparting substantially increased waterresistance, and admixing and shearing said components until a water-resistant grease of the desired consistency is obtained.

In order to aid in the understanding of the inventive concept, the following additional disclosure is submitted. Unless otherwise indicated, all parts and percentages are by weight rather than by volume.

(A) ALKOXYLATED ADDITIVES IMPARTING WATER-RESISTANCE TOGREASES These are selected from the group consisting of:

(1) Polymeric alkoxylated derivatives of alcohols These novel additives, which are used to impart increased water-resistance to grease thickened with alkali metal soaps, are known compositions which can be purchased or prepared by the methods disclosed in the patent or technical literature. See, for example, the preparation of a copolymer of polyoxyethylene and polyoxypropylene glycol having a molecular weight from 300 to 15,000 as disclosed by Toussaint et al. in US. Pat. No. 2,425,845 2 and Roberts et al., in US. Pat. No. 2,425,755, both assigned to Carbide & Carbon Chemicals Corp. These novel grease additives may be obtained among other preparative methods using the aforementioned process of Toussaint et a1. and Roberts et al., by the alkaline catalyzed reaction in a substantially anhydrous environment of a mixture of ethylene and 1,2 propylene oxides with alcohols, diols and/or polyols, or their mixtures, at temperatures ranging from about C. to 160 C. Typical alcohols, diols and polyols include methanol, n-butanol, n-octanol, ethylene glycol, propylene glycol, glycerol and sorbital, among others. The average molecular weights as measured by the ebullioscopic method or calculated from viscosity measurements or acetyl values are between about 300 to about 15,000. The favored copolymers usually contain from about 50 to 75 parts by weight of propoxy groups, and from about 25 to 50 parts by weight of ethoxy groups and have an average molecular weight of from about 1500 to about 10,000. One of the preferred copolymers is sold by Retzloif Chemical Company of Houston, Tex., as DPG-lS. It contains about 75 to parts by weight of propoxy groups and from about 25 to 10 parts by weight of ethoxy groups.

The novel copolymer additives are employed in an amount effective to substantially increase the resistance of the alkali metal soap-thickened grease to the attack by water. This amount will vary according to the additive employed, the degree of protection sought, the alkali metal soap contained in the grease, etc. However, when lithium soaps are used to thicken a mineral oil base and the preferred copolymers are derived from alkoxylation of di-, tri-, or polyhydroxylated compounds, from about 0.1 part by weight to 5.0 parts by weight of copolymer per hundred parts by weight of the finished grease represents the extremes of the polymer content. A more useful range of about'0.l to 0.6 part by weight of copolymer produces greases which have good properties and consistently pass the water-resistance tests, and for this reason are preferred.

Alcohols as used herein not only refer to aliphatic compounds containing at least one free-hydroxyl group but which as1 can be seen from supra also includes diols, trials and p0 yols. i 2 While the polymeric compositions noted above are not novel per se, their utilization in small quantities (i.e., from 0.1 to 5.0% by weight of the total grease composition) as additives in grease to effect a substantial increase in the re sisting of the greases to water is believed to be novel.

3 (2) Alkoxylated adducts of alkylated phenols The second class of additives employed to provide improved water-resistance to alkali metal, particularly lithium, soap-thickened greases comprises alkylene oxide adducts of alkylated phenols. The favored alkylene oxides are ethylene oxide, propylene oxide and their mixtures. A favored group within the class are alkylated phenols wherein the alkyl group contains 5 to 15 carbon atoms, which have from 2 to 50 alkoxylate groups attached to the molecule. The preferred additives within this class are ethoxylated phenols whose alkyl groups contain 6 to 10 carbon atoms and an average of 5 to ethoxylate groups per molecule.

Two of the preferred ethoxylated alkylated phenols are commercially available. One of these is a nonyl phenol ethoxylated with an average of 9.5 moles of ethylene oxide per mole of nonyl phenol. The second phenolic adduct which is preferred is supplied by the Retzloif Company of Houston, Tex., and is designated as DRE-203.

(3) Mixed alkoxylated products of alkylene diamines The third class of additives which impart substantially improved water-resistance to greases refers to products formed by initially adding an alkylene oxide such as ethylene or propylene oxide to an alkylene diamine such as ethylene diamine (H NCH CH H N) to give the symmetrical tetrapropoxylated derivative followed by subsequent oxyethylation to a structure shown below:

wherein x=an integer ranging from 6 to 16.

These condensates are also available commercially from the Petrolite Company of Houston, Tex. A favored additive is referred to by the manufacturer as Tretolite Additive A-3089 whose active components structure appears above.

(B) LUBRICATING OILS The lubricating oils employed as the base fluids in this invention of prime interest are the natural (mineral) oils, or mixtures of one or more of these oils. The mineral oils which can be used are those of paraflinic, naphthenic, asphaltic or parafiinic-asphaltic type derived from crude oils by refining processes including distillation, cracking and/or polymerization. These oils will have a gravity (API) of about 10 to 35, a viscosity within the range of 100 to 2000 SUS at 100 F. and flash points within the range of about 275 F. to 650 F. Generally a viscosity of from about 700 to 1400 SUS at 100 F. is favored.

The lubricating base oils preferred for the grease formulations are mineral oils of the paraflinic type having SUS viscosities at 210 F. in the range of about 75 to 95 and flash points in the range of about 450 F. to 600 F. The above oils are preferred as bases for greases because they consistently produce greases having the desired enhanced resistance to water.

(C) OPTIONAL GREASE ADJUVANTS 575i50 cs.; form-liquid; specific gravity-4.02 at 60 F.; pour pointbe1ow =5 R; mole wt.ti09Q-8000.

deleterious properties. These adjuvants can be of diverse structure or origin and are typified by the following: extreme pressure (E.P.) agents such as the metallic naphthenates and sulfurized sperm oil, fillers such as the metal oxides, oxidation inhibitors including phenyl-beta-naphthylamine and the diphenyl amines, corrosion inhibitors including alkali metal nitrites, and stabilizers such as the fatty acid esters. When these optional adjuvants are employed they are used in minor amounts, seldom totaling more than 10 percent by weight of the finished grease. More usually these adjuvants comprise from about 0.5 to 7.0 parts by weight per hundred parts by weight of finished grease. Ordinarily, these adjuvants are added at the expense of the oil base, most often during the cooling step that takes place during the finishing of greases.

(D) ALKALI METAL AND CALCIUM SOAPS The soap-thickeners of prime interest in the formulation of the water-resistance greases of this invention include lithium soaps and, to a lesser extent, calcium and lithium soap mixtures. The additives are particularly use ful in lithium based greases because they require the addition of water-resistant additives for superior waterresistance and because they presently are of the greatest commercial importance. Ordinarily it is convenient to use soaps formed in situ, the alkali metal soaps being formed by saponifying at least one suitable saponifiable material with an alkaline form of the metal. The term saponifiable materials refers to fatty acids and hydroxysubstituted fatty acids, especially those containing from about 12 to 32 carbon atoms per molecule. Also included are glycerides or hydroxylated glycerides. Suitable saponifiable materials include the following illustrative materials: methyl-lZ-hydroxystearate, 12-hydroxystearic acid, stearic acid, hydrogenated castor oil, myristic acid and the like.

The preferred saponifiable materials in the order of preference are the esters of 12-hydroxystearic acid, 12- hydroxystearic acid, and stearic acid and/or their mixtures. In one favored composition, the saponifiable material comprises 30 to 50 parts by weight of methyl 12- hydroxystearate and 70-50 parts by weight of 12-hydroxystearic acid.

(E) PROCESSES FOR PREPARING THE NOVEL LOW WATER ABSORBING GREASES At least three process variations are convenient. In one favored process, the additive imparting water-resistance is added to a preformed alkali metal soap-thick ened grease such as is typified by a mineral oil based grease already containing a lithium soap of 12-hydroxystearic acid. In this procedure, the preformed grease containing some or none of the optional additives, such as extreme pressure additives, is heated to about 200 to 400 F. to bring it to a fluid state. During this heating step the preformed grease (as illustrated by lithium soapthickened grease) is continuously stirred. The grease is then cooled to about to 240 F., preferably from about 180 F. to 200 F. At this time during the cooling step, the additive imparting water-resistance is added along with any other compatible additives. The charge is held for about 30 minutes at this temperature range and then brought to the desired consistency by milling.

A second favored procedure comprises forming the grease in situ. In this procedure an aqueous solution of the alkaline lithium compound, the saponifiable (fatty) material, and part of the mineral oil is charge to a kettle equipped with heating, cooling and stirring means. The batch is heated to between about 180 and 225 F. and held at this range for about to 2 hours, then heated to between 250 F. and 350 F. with stirring to dehydrate the grease while slowly adding the remaining oil. At the end of this time, the grease mixture is cooled to about 180 to 220 F. while stirring and at least one waterresistant additive, as well as optional additives, are added until a homogeneous mixture is obtained. A sample is taken for testing and milled to the desired consistency using a colloid mill.

A third favored procedure which can be utilized in formulating the water-reistant greases of this invention is performed as follows:

(1) A grease kettle fitted with stirring, heating, cooling and circulating means is charged with the following components:

(a) all of the alkaline material such as lithium hydroxide in aqueous or alcoholic form,

(b) from about one-third to one-half of the paraffinic oils to be added,

(c) all of the saponifiable material (such as methyl-12- hydroxystearate) employed.

(2) Stirring and heating to 180 to 200 F. and holding the stirred batch at this temperature range for at least one hour.

(3) Heating while stirring up to about 375 to 425 F. When the temperature reaches 320 to 330 F., adding from one-fifth to one-eighth of additional parafiinic oil (or mixture of oils) at a rate of 0.40 to 0.60 part by weight per minute.

(4) When the batch temperature reaches between 375 to 425 F. and the mixture is completely fluid, the heating is stopped and about one-eighth to one-tenth of the mineral oil (or a mixture of oils) is added to quickly cool the mixture to about 360 to 375 F.

(5) The mixture is then allowed to cool at a rate of about 1 F. per minute until the batch temperature reaches about 320 F.

(6) At this point, the remaining mineral oil (or-a mixture thereof) is slowly added with stirring to the cooling batch to further lower the temperature to about 180 F. to 200 F. until all of the oil is added.

(7) While holding the stirred batch between 180 and 200 F., all of the additives, including the additives imparting water-resistance to the grease, are added and.

mill set ,claimed and disclosed in US. 3,475,335 and 3,475,337,

(F) EVALUATION METHOD The following procedure is used as the criterion for improvement in water-resistance.

(1 Procedure A 20 gram sample to be tested is weighed into a cylindrical brass cup equipped with a stirrer. The stirrer is rotated at 1200 r.p.m.- *-60 r.p.m., while adding 2 ml. increments of distilled water from a burette. After stirring for a one minute period the grease is examined for evidence of free water. If no evidence of free water appears, an additional 2 ml. increment of water and stirring is continued for a further minute. The procedure is re-- peated until free water is evident after the one minute stirring period. Then the grease is stirred for an additional four minutes (making a total working time of 5 minutes). If free water is not evident at the end of the additional 4 minutes stirring, another 2 ml. increment of water is added and the operation is continued.

Make the final reading when free water is evident after a total working time of 5 minutes. At this point, record the number of ml. of distilled water added for the calculation of end point.

The color, texture and/ or consistency of the grease are recorded at the end point. These values are compared Pour point with the original sampleaThe calculated end point is determined as follows:

' m1. of water added p wt. of sample IllustrationEight (8) ml. of water is added.

End point= =40 water adsorbed If there is no free water evident at the end of the stirring period for the 10th increment, the test is discontinued and the end point is recorded as 100+. It is optional to continue for a total of 15 increments of water. If no water is evident after 15 additions of water, then record the end point as (G) PREFERRED WATER-RESISTANT GREASES The lithium and mixed calcium-lithium soap-thickened greases having the following components in the proportions indicated are given below.

Components of grease I: Parts by weight (1) Lithium 12-hydroxystearate 5.0-10.0 (2) Calcium l2-hydroxystearate 3.4-5.5 (3) Lead napthenate 1.0-2.0 (4) Lead diamyldithiocarbamate 0.5-1.5

(5) Antimony dialkyldithiocarbamate 0.1-1.0

(6) Polymeric alkoxylate copolymer 0.1-1.0

(7) Mineral oil 82.0-93.0

. Components of grease II:

(1) Lithium l2-hydroxystearate 5.0-l0.0 (2) -Lead-naphthenate 1.0-2.0 (3) Ethoxylated nonylphenol containing an average of 9.5 ethoxylate groups per molecule 0.l-l.0 (4) Antimony dialkyldithiocarbamat 0.25-1.0 (5) Lead diamyldithiocarbamate 0.25-1.0

(6) Mineral oil 82.0-93.0

Components of grease IE:

(1) Lithium 12-hydroxystearate 5.0-10.0 (2) Lead naphthenate 1.0-2.0 (3) Lead diamyldithiocarbamate 0.25-l.0 (4) Antimony dialkyldithiocarbamate 0.1-1.0 (5) Mineral oil 82.0-93.0 (6) Oxyalkylated condensation products of phenols 0.1-1.0

In order to described this invention in the greatest possible detail, the following illustrative examples are submitted. Unless otherwise indicated, all parts and percentages are by weight rather than volume.

EXAMPLE 1 Preparation of a lithium soap-thickened grease having enhance water-resistance A grease kettle equipped with heating, cooling and stirring means is charged with 5.5 parts by weight of a 9.5 percent by wt. aqueous solution of lithium hydroxide, 6.2 parts by weight'of the methyl ester of 12-hydroxystearic acid and 76.70 parts by weight of mineral oil base A. The batch is heated to F. with stirring, held at this temperature for 1 hour, then heated with continued stirring at 325 to dehydrate the grease.

While the batch is held at the dendration temperature,

" Mineral 011 base A has the following properties ARI gravity 18.1 Viscosity SUS at 100 F. 100 Viscosity SUS at 210 F. 210 Flash point (COC) F.-- 505 41.47 parts by weight of mineral oil base B is added to the stirred mixture at the rate of 0.5 part by weight per minute. When the oil addition is completed the stirred batch is cooled to 195 F. at the rate of 1 F. per minute and a total of the following additives are added at 195 F.-1.95 parts by weight of lead naphthenate, 1.3 parts by weight of lead diamyldithiocarbamate, 0.65 part by weight of antimony dialkyldithiocarbamate and 0.13 part by weight of a copolymer of polyoxyethylene and polyoxypropylene. After stirring, to ensure homogeneity, a grease sample is taken for testing and is milled to the desired consistency using a colloid mill. Upon testing, the data which appears in Table I are obtained.

EXAMPLE 2 Preparation of a control batch of a lithium soapthickened grease without water absorption additive A grease formulation substantially similar in content and formulation to that described in Example 1 is prepared using a grease kettle equipped as described. The sole diiference between the content of the two greases is that whereas 0.13 part by weight of a copolymer of polyoxylethylene and polyoxypropylene are added to the grease composition of Example 1 along with the other TABLE I Example golysoxyalkylene copolymer, parts by wt. 0. 1 0. 00

Penetration:

Unworked 341 325 orked 320 312 Worked, 10,000 strokes (fine hole worker) 322 324 Dropping point, F 372 360 Water absorption, percent: 150+ Original penetration 309 322 Penetration of emulsion 317 343 Timken, O.K. load, lbs- 60 Load wear index. 41. 8 42. 8 Four ball wear, (2 hr., 20 kg., 1,800 r.p.m., 130 F.):

Scar diameter in mm 0. 59 0. 60

EXAMPLES 3-12 Effect of varying the concentration of the copolymer of Example 1 The purpose of these examples is to determine the minimum eifective quantity of copolymer in lithium soapthickened, preformed grease. In all instances the copolymer was added to the stirred preformed grease at 190 F.-200 F. The concentrations studied varied from 0.1 part by weight to 1.0 part by weight. As the data of Table II indicate the minimum effective quantity is 0.10 part by weight with the upper limit being primary limited by economics.

TABLE II.--COMPOSITION AND TEST RESULTS QF LITHIUM-SOAP THICKENED BATCHES USING VARYING QUANTITIES OF ADDITIVES OF EXAMPLE 1 Evaluation of lithium thickened greases Example 3 4 5 6 7 9 10 11 12 Parts by wt.:

Li-12-OH-stearate 3. 00 3. 00 3. 00 2. 99 2. 99 2. 98 2. 97 2. 96 2. 96 2. 90 Residual naphthenic oil 70. 39 70.31 70. 23 70. 18 70. 11 70.05 69. 98 69. 92 69. 85 69. 77 Paraifinic oil 17. 59 17. 57 17. 17. 54 17. 53 17. 51 17. 49 17. 48 17. 46 17. 44 Sulfun'zed sperm oil 7. 00 7. 00 6. 98 6. 98 6. 97 6. 96 6. 96 6.96 6. 96 6. 95 Lead naphthenate 1. 40 1. 40 1. 40 1. 40 1. 39 1. 39 1. 39 1. 38 1. 37 1. 36 Diphenylamine 0. 50 0. 50 0. 50 0. 50 0. 50 0. 50 0. 50 0. 49 0. 49 0. 48 Copolymer Ex. 1 0. 10 0. 20 0. 30 0. 40 0.50 0. 0. 0. 0.90 1.00 Free LiOH- 0. 02 0.02 0. 02 0. 01 0. 01 0.01 0. 01 0.01 0.01 0. 01

Tests:

Penetration at 77 F.: Worked 60 strokes 330 0 328 331 331 329 6 342 325 331 Water absorption test: Water absorbed, percen 150+ 70 80 40 50 35 60 45 00 Original pene. 302 305 3 02 298 302 298 317 302 305 294 Pene. 0t emulsion 9 459 377 377 339 335 328 362 347 332 354 Pene. change, ASTM points +157 +72 +75 +41 +33 +30 +45 +45 +33 +00 1 Whose major properties are: Gravity API, 24.5; SUS at 210 F., 106; Viscosity index, 73;

residue (conradson), 1%

I Converted from scale penetration.

5 Mineral oil base B has the following properties:

API gravity -2 Viscosity SUS at F. N 100.0 Viscosity SUS at 210 F. 38.7 Flash point (000) F. 365 Pour point F." +15 The copolymer has the following properties: Physical state at 77 F Liquid pH, 5% solution in 3: 1 H2O/IPA 6.8 Pounds per gallon at 77 F. 8.5 Flash point, F. (TOC) Viscosity, cps. at 77 F., Brookfleld 4.50 Specific gravity 1.020 Mole weight 2300-2500 1,2 oxypropylene to oxyethylene ratio 80:20 R at e s l bil ty nu ber '--?-.-:-:-r.-:r::-:::-::-e===- 14.1

Pour point, 5 F; Flash point F. (000) 470 F.; Carbon Fwhose major properties are: Gravity .API, 30; SUS at 100 F., 182; SUS at 210 F., 40; Viscosity index, 87; Pour point, 0 F.; Flash point (000),

EXAMPLE 13 Preparation of another water-resistant grease using an ethoxylated alkylated phenol (DRB-203) to impart water resistance In this experimental work a lithium soap-thickened grease is prepared using a preformed grease which has been made by the third process described in column 5, lines 6-8. The product contained 0.5 part by weight of an ethoxylated alkylated phenol (DRE-203) substituted for the copolymer of Examples 3-12. As the data of Table III show, a grease with good general properties and excellent water resistance is obtained.

EXAMPLE 14 Preparation of another water-resistant grease using alkoxylated adducts of alkylated phenols to impart water resistance In this experimental work a lithium soap-thickened grease was prepared using the process and mineral oils disclosed in Example 1. The product contained 2.0% by weight of the oxyethylene adduct of nonylphenol containing an average of 9.5 moles of ethylene oxide in the molecule. As the data of Table III show, a grease with good general pro erties and water-resistance is obtained.

9 EXAMPLE 15 Preparation of another water-resistant grease using a mixed alkoxylated alkylene diamine to impart water resistance to the grease In this procedure the materials and the process techniques of Examples 3-12 are used to produce a lithium soap-thickened mineral oil based grease except that 0.5 part by weight of the following additive is used to replace the copolymer additive. The structure is shown below.

TABLE 111 Example 13 Example 14 Example 15 Water resistance additive, wt.

percent None None None E t i i l a 1 h 1 oxy ate nony n mm 2.0 Alkoxylated alkylene diamine- 0. 5 Tests:

Penetration:

Unworked 284 283 362 315 280 266 Worked 264 265 324 315 271 266 Worked 10,000 strokes (fine hole Worker) 297 275 325 339 305 287 Dropping point, F 388 385 360 384 390 Waterabsor tion, percent. 80 40 175 30 150 30 Origina penetratiom- 263 258 334 311 249 249 Penetration of emulsion 297 285 383 330 343 290 Timken, O.K. Load, lbs.. 40 45 Load wear index 36. 5 38. 0 Four ball wear (2 hr., kg., 1,800 r.p.m., 130 F.): Scar diameter, mm. 0.45 0. 34

H(0CH;CH1), OCHzH 4 CHCHgO 4-(CH5CH30);H

N-CHzCHz-N H(O CH;CH;)X( 00m? (OHCH O )(-(CH2CH30);H CH3 4 CH:

wherein x=an integer ranging from 6 to 16. Again, Table III summarizes the data obtained.

EXAMPLE 16 Preparation of a preferred water resistant lithium-calcium thickened grease using the additive of Example 1 In this procedure, the preformed grease process disclosed in Examples 3-12, 14 and 15 is employed but a difierent base grease is used. A mixture of lithium and calcium-l2-hydroxystearate soaps is used to thicken the oil base and 0.5 part by weight of the copolymer additive utilized in Example 1 is employed. The composition after formulation is shown below.

Components: Parts by weight 1 Lithihum-12-hydroxystearate 8.7 (2) Calcium-l2-hydroxystearate 4.4 (3) Lead naphthenate 1.5 (4) Lead diamyldithiocarbamate 1.0 (5) Antimony dialkyldithiocarbamate 0.5 (6) Copolymer additive of Example 1 0.5 (7) Naphthenic residuum* 1.0 (8) Paraflinic oil E** 28.8 (9) Prafiinic oil F*** 53.6

Total 100.0

'See the following table:

1st parat- 2d paraf- Naphthenlc 011 properties finic oil" finic oil Gravity API 183 21. 5 2e. 5 Flash (000), F 600 480 490+ Viscosity sUs at 210 F 680 77 77 Pour point, F +60 +5. 0

As the data in Table IV, which follows, indicate, a water resistant grease having excellent general properties is formed.

10 TABLE IV Properties of the grease prepared in Example 16 Properties: Grease, Example 16 Odor Oily. Appearance Brown, buttery very slt. mealy. Penetration- Unworked 303. Worked 313. 10,000 stroke (FH) 297. Percent change 5.1. Shell roll, D-183l-- Points change -26. Percent change 8.4. Dropping point, F. 375. Water washout- F., percent 2.5. 175 F., percent 2.6. Water absorption, percent 75. Penetration- Original 287. Emulsion 287. ASTM bomb oxidation,

p.s.i. drop at 100 hrs. 1.0. AST M wheel bearing- Weight loss, g Trace. Weight loss, percent. US. Steel Bleeding and Evaporation Test, 50 hrs. at 212 F.-

Bleeding, percent 8.8; 7.4. Evaporation, percent 0.33; 0.28. US. Steel Pressure Oil Separation Test- Bleeding, percent 8. Penetration-t Original 29 Filter cake Percent of original 64- U.S. Steel Grease Mobility Test, F., p.s.i., g.. flow/sec. 0-05- 4 Ball Wear; 1 hr.; 130 F.; 1800 r.p.m. 20 kg.; scar As the preceding examples and discussion have indicated, the subject invention ofiers numerous advantages. For example, relatively small quantities of readily available, inexpensive additives, particularly the polymeric alkoxylated derivatives of alcohols, polyols and the like substantially improve the resistance of alkali metal lithium soap-thickened greases to water. This is also true in the instance of the mixed lithium and calcium soapthickened greases which are prone to attack by water. The inclusion of as little as 0.10 part by weight additive per hundred parts by weight of the finished grease (especially the polymeric ethoxylated derivatives of polyethylene and/ or polypropylene glycols) not only substantially improves the water-resistance of lithium soap and mixed lithium and calcium-soap thickened greases but does so without compromising the desirable characteristics of the lubricant products.

While the novel additives of this invention are known as compositions of matter and have been employed as one of the major components of lubricating oils, insofar as is known they have not been used as additives in minor concentrations in lithium soap and/or lithiuml-calcium thickened lubricants. For example, in US. Pat. 3,472,781 the polymeric alkoxylated polyol derivatives are advocated as lubricants in hydraulic fluids. When used for this purpose they have been used in much higher concentrations (col. 2 line 9) ranging from 1 to 30 percent. In contrast, as indicated supra the inventive additives need be present in only minor proportions. Therefore, it was quite unexpected to find that for the purpose of this invention, the additive functioned well at much lower concentration levels. This discovery was empirically derived and could not have been predicted.

Finally, the subject invention is relatively flexible insofar as several preparative processes can be employed, the mineral base oil employed and the ancillary additives are concerned. The metes and bounds of this invention are best ascertained by an examination of the claims which follow, read in conjunction with the preceding specification.

What is claimed is:

1. A lithium soap or a lithium soap-calcium soap thickened mineral oil based grease having improved resistance to water comprising the following admixture of components in the following proportions:

(a) from about 80 to 97 parts by weight of at least one mineral oil of lubricating viscosity,

(b) from about to 2 parts by weight of a soap selected from the group consisting of lithium soaps and mixtures of lithium soaps and calcium soaps,

(c) from about 5.0 to 0.1 parts by Weight of at least one alkoxylated additive imparting water-resistance to said greases, said additives being selected from the group consisting of alkoxylated alkylated phenols and alkoxylated alkylene diamines.

2. The grease of claim 1 in which each 100 parts by weight of grease contains from about 0.5 to 7.0 parts by weight of grease adjuvants.

3. The grease of claim 1 wherein the additive is alkoxylated alkylphenols.

4. The grease of claim 1 wherein the additive is alkoxylated alkylene diamines. I

5. The grease of claim 1 wherein the soap is a lithium soap.

6. The grease of claim 1 wherein the soap is a mixture of lithium and calcium soaps.

the reaction of alkaline forms of lithium and/or calcium metal compounds with a saponifiable material selected from fatty acids, hydroxy-substituted fatty acids, glycerides and hydroxylated glycerides, (c) from about 5.0 to 0.1 parts by weight of alkoxylated additives imparting water-resistance to said greases, said additives being selected from the group consisting of ethoxylated alkylated phenols and ethoxylated and propoxylated alkylene diamines. 8. The grease of claim 7 wherein the soap is lithium 12-hydr0xystearate.

9. The grease of claim 7 wherein the soap is a mixture of lithium and calcium 12-hydroxystearates.

References Cited UNITED STATES PATENTS Bondi 252--40.7 Bondi 252- '.7 Moore et a1 25240.5 Scott 252-40.5 Farmer et al. 252405 Greenwood et a1. 252-40.7 Horth et a1. 25240.5 Morway 25242 Kress et al 25252 A Rossimann 25252 A DANIEL E. WYMAN, Primary Examiner I. VAUGHN, Assistant Examiner US. Cl. X.R.

233 UMTED STATES PATENT ()FFICE CERTIFICATE OF CORRECTION Patent No. 3,301,506 Dated April 2, 19m

Inventofls) Edward A. Cross and Gordon S. Bright It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3', line 73, reading "cs." should read --ctks,-.

Column 3 line 75, reading "Pour-Po nt Below 53F? should read Pour Point, F-Bel ow 5F,----.

Colwm'6, line 72, reading "Viscosity SUS at 100F.....100"

should read Viscosity SUS at 100F. .700

Column 6, line 7 reading Viscosity SUS at 210F. 2l0" should read Viscosity SUS at 210F. .205

001mm 7, line 65, reading "Viscosity sus at lO0 F.N" should read Viscosity SUS at lO0F Column .9, line 21 under Exanple 1n, reading "325" should read 352 y v Signed and sealed this 19th day of November 1974..

( EA Attest: Y

MCCOY M. GIBSON JR. c. MARSHALL DANN Attesting Officer Commissioner of Patents