US3919093A - Lubricant compositions containing alkylene oxide polymers and sulfur - Google Patents

Abstract

Lubricant compositions are provided containing anti-wear amounts of mixtures of an alkylene oxide polymer and sulfur.

Description

United States Patent [1 1 Davis et al.

l l LUBRICANT COMPOSITIONS CONTAINING ALKYLENE OXIDE POLYMERS AND SULFUR [75] Inventors: Robert H. Davis, Pitmzm; Edward A.

Oberright, Woodbury; John W. Schick, Cherry Hill, all of NJ.

[73] Assignee: Mobil Oil Corporation. New York 5 Nov. 11, 1975 {56] References Cited UNITED STATES PATENTS 3130.159 4/1964 SIedIHUmWm, I. 351 31 FOREIGN PATENTS OR APPLICATIONS 45l.372 8/1936 UniIed kingdumumm... 352/.

Prinmry Erumiuer-Delbert E. Gantz .-lssisrunt Emmiucr-J. Vaughn Almrucy. Agent, or FirmCharles A, Huggett; Rurmond W. Barclay; Benjamin I. Kaufman [57] ABSTRACT Lubricant compositions are provided cnnlaining unliwealr amounts of mixtures of an ulkylene oxide pol)- mer and sulfur.

[5 Claims. N0 Drawings LUBRICANT COMPOSITIONS CONTAINING ALKYLENE OXIDE POLYMERS AND SULFUR BACKGROUND OF THE INVENTION cant compositions, such as lubricating oils and greases, 0

which normally exhibit wearing effect on machinery with which they may come into contact and, in some instances, even result in welding action.

2. Description of the Prior Art The prior art has long recognized that lubricant compositions such as lubricating oils (including mineral oilbased and synthetic oil-based compositions) and greases, exhibit wear and even welding effects on metal parts with which they may come into contact in performing their function as lubricants. In this respect, alkylene oxide polymers, for example, fatty alcohol polyglycol ethers have been suggested for use as anti-wear agents in lubricating compositions, but 'have been found lacking in exhibiting a relatively high degree of anti-wear effect and, in some instances, have also exhibited welding effects.

Of particular significance, insofar as the lubricant compositions of the present invention are concerned, is the ability to improve the anti-wear properties of lubricating media which may comprise liquid hydrocarbon oils, in the form of either a mineral oil or a synthetic oil, or emulsions or in the form of a grease in which any of the aforementioned oils are employed as vehicles. In general, mineral oils, employed as the lubricant or grease vehicle, may be of any suitable lubricating viscosity range as, for example, from about 45 SSU at 100F. to about 6,000 SSU at I00F., and preferably, from about 50 SSU at 2l0F. to about 250 SSU at 210F. These oils may have viscosity indexes varying from below 0 to about I00 or higher. Viscosity indexes from about 70 to about 95 are preferred. The average molecular weights of these oils may range from about 250 to 800. Where the lubricant is to be employed in the form of a grease, the lubricating oil is generally employed in an amount sufficient to balance the total grease composition after accounting for the desired quantity of the thickening agent and other additive components to be included in the grease formulation.

In instances where synthetic oils, or synthetic oils employed as the vehicle for the grease, are desired in preference to mineral oils, or in combination therewith, various compounds of this type may be successfully utilized. Typical synthetic vehicles include polyisobutyiene, polybutenes, hydrogenated polydecenes, polypropylene glycol, polyethylene glycol, trimethylol propane esters, neopentyl and pentaerythritol esters, di(2-ethyl hexyl) sebacate, di( 2-ethyl hexyl)adipate, di(butyl phthalate), fluorocarbons, silicate esters, silanes, esters of phosphorous-containing acids, liquid ureas, ferrocene derivatives, hydrogenated mineral oils, chain-type polyphenyls, siloxanes and silicones (polysiloxanes), alkyl-substituted diphenyl ethers typified by a butylsubstituted bis (p-phenoxy phenyl) ether, phenoxy phenylethers, etc.

SUMMARY OF THE INVENTION It has now been found that increased anti-wear, and even anti-weld properties can be imparted to lubricant 2 compositions by incorporating therein mixtures of alkylene oxide polymers and sulfur.

In general, the alkylene oxide polymers, which are commercially available anti-wear agents, can be prepared by the reaction of from 1 to 30 moles of an alkylene oxide with from to 99 moles of an alcohol, amine, amide, organic acid, phenol or mercaptan.

The sulfur employed in the novel mixtures of the present invention may comprise elemental sulfur or a sulfur-containing material or sulfur compound. The term sulfur is intended to include elemental sulfur as well as organic sulfur compounds. Insofar as elemental sulfur is concerned, this is intended to include sulfur powders having any of the allotropic forms and flowers of sulfur. In addition, alkyl sulfides may be employed including dialkyl and disulfides, unsymmetrical alkyl sulfides, disulfides and polysulfides in which the alkyl groups have carbon atoms ranging from I to 20. There may also be employed aromatic sulfides including phenyl sulfides and substituted-aryl polysulfides. Particularly preferred of the aromatic sulfides is dibenzyl disuIfide. These sulfides may contain up to about l0 atoms of sulfur per mole of sulfide. Also included in the sulfur compounds, that may be employed in the synergistic mixtures of the present invention, are those described in U.S. Pat. No. 2,993,858.

In general, the aforementioned alkylene oxide polymers and sulfur may be employed in any desired proportion. For most applications, the sulfur in the mixture can be employed in an amount from about .01 to about l5%, and preferably, in an amount from about 0.05 to about 5%, by weight, of the total weight of the mixture. Furthermore, the mixture itself, for most applications, may be employed in the lubricant composition in an amount from about 0.1 to about 30%, and preferably, in an amount from about 3 to about 10%, by weight, of the total weight of the lubricant composition.

DESCRIPTION OF SPECIFIC EMBODIMENTS In order to demonstrate the improvement in metalcutting activity realized by employing the abovedescribed novel mixtures in lubricant compositions, compared with that realized by employing anti-wear components of the above-described mixtures, individually, comparative data were obtained as shown in the examples of the following tables.

The data were obtained by means of a Tapping Efficiency Test and, in general, the procedure of this test involves measurement of torque developed in an internal threading operation employing SAE 1020 hotrolled steel. In this test, thirty torque values are obtained with the test fluid and compared with thirty reference fluid values to obtain Tapping Efficiency i.e.

Ave. 30 Reference Fluid Torque Values X 100 Ave. 30 Test Fluid Torque Values 5% Tapping Efficiency drill press equipped with a table which is free to rotate about the center on ball-bearings. A torque arm is attached to this floating table" and the arm in turn activates a spring scale, so that the actual torque during the tapping. with the oil being evaluated, is measured directly. The same conditions used in evaluating the test oil are employed in tapping with a strong oil which has arbitrarily been assigned an efficiency of 100%. The average torque in the test oil is compared to that of the standard and a relative efficiency is calculated on a percentage basis. For example.

Torque with standard reference oil 19.3 Torque with test oil 19.8 Relative efficiency of test oil l9.3/l9.8 X 100 97.4

This test is described by C. D. Flemming and L. H. Sudholz in Lubrication Engineering. volume 12, No. 3,

May-June I956. pages 199 to 203, and also in US. Pat. 2

4 It should be noted. in accordance with the foregoing Tapping Efficiency Test that it" the test fluid torque values exceed the reference value. Tapping Efficiency is below 100%. Criteria for product acceptance are evaluated as follows:

Tapping Efficiency Comments 100; Fluid considered outstanding and should outperform reference product in severe cutting operations. Acceptable range for moderate duty cutting fluids.

All products with Tapping Efficiencies below 80% are considered unacceptable. Torque values are erratic. frequently due to tap stickin; and/or breakage.

Employing the foregoing parameters the following data were obtained with comparisons to sulfur and a variety of allcoxylated materials.

TABLE I Tapping Test Results Emulsifiable, Oil Dispersible Ethylene Oxide Polymers Plus Sulfur Z wL-sulfurized Tapping I50 SUS at l00F. Efficiency Z Cl WL-l 50 SUS at Paraffinic Oil SAE I020 Example Additive 100F. Paraffinic Oil (0.601 Added S.) H.R. Steel l Reference Fluid A l00 80 2 Reference Fluid B I00 87 Ethylene Oxide Amine 3 Ethylene Oxide Oleylaminc 7 78 4 7 I03 Ethylene Oxide Amide 5 Ethylene Oxide Olcylarnide 7 76 6 7 1 l5 Ethylene Oxide Mercaptun 7 Ethylene Oxide Dodecylmercaptan 7 69 8 7 I09 Ethylene Oxide Acid 9 Ethylene Oxide Oleic Acid 7 82 ll) 92 Ethylene Oxide Phenol l l Ethylene Oxide Octylphenol 7 75 I2 7 99 Ethylene Oxide Alcohols l3 Polyoxyethylene Oleyl Ether 7 8] l4 7 [26 I5 Polyoxyethylcne Cetyl Ether 7 77 I6 7 H3 l7 Polyoxyethylene Lauryl Ether 7 76 '8 7 I l5 l9 Ethoxylatcd Castor Oil 7 92 7 W6 TABLE ll Tapping Test Results Non Emulsive. Oil Soluble Alkylene Oxide Polymers Sulfur k Wt. Sulf. I SUS at l00F. Tapping Elfic. 1' Wt. 150 SUS at Paraffinic Oil '1, SAE I020 Example Additive l00F. Paraffinic Oil (0.68% Added S.) H.R. Steel lmides Prepared from Polybutenyl Succinic Anhydride 8t Amino Polyoxypropylene Polymers 2! 2M polybutenyl succinic anhydride 22 73 (2300 MW) lM diamino polyoxypropylene (2000 MW) 22 1 L54 l03 23 lM polybutenyl succinic anhydride 7 (1200 MW) IM diamino polyoxypropylene (2000 MW) Complex Esters 24 Prepared via reaction 7 72 Azelaic Acid/Propylene Oxide/ lsooctanol TABLE Il-continued Tapping Test Results Non Emulsive, Oil Soluble Alkylenc Oxide Polymers Sulfur Z Wt. Sulf. I50 SUS at 100F. Tapping Effic. 71 Wt. 150 SUS at Paruffinic Oil it, SAE I020 Example Additive lOll'F. Paral'finic Oil (0.68% Added 5.) H.R. Steel Azelaic Acid/Propylene Oxide) 7 I08 Isnoctanol From Table I, as shown by Examples 3, 5, 7, etc., it will be noted that all sulfur-free ethoxylated materials would be considered unsatisfactory lubricants when added to mineral oil. However, if these materials are combined with sulfur. as shown by Examples 4, 6, 8, etc. tapping efficiencies greatly exceed values obtained for sulfurized mineral oil. It should also be noted that all compositions described in Table I, Examples 3-20, are emulsifiable, i.e., they can be used in the neat form or combined with water to form an emulsion which can exhibit lubricating properties. This emulsifiable tendency is desirable for many applications. However, the ability to combine with water may be undesirable in situations where corrosion and/or lube oil reclamation problems are involved. In order, therefore, to minimize this tendency for ethoxylated additives to combine with water, a number of alkoxylated compounds were synthesized involving imide and ester formations. A summary of the tapping results obtained from these nonemulsifiable oil soluble products are shown in Table II. In every instance cutting efficiency was improved when these compounds were combined with sulfur.

While this invention has been described with reference to preferred compositions and components therefor, it will be understood by those skilled in the art that departure from the preferred embodiments can be effectively made and are within the scope of the specification.

We claim:

I. A lubricant composition containing an anti-wear amount of a mixture of an alkylene oxide polymer and sulfur.

2. A lubricant composition, as defined in claim I, wherein said alkylene oxide polymer comprises the reaction product of about I to about moles of an alkylene oxide and about 70 to 99 moles ofa member of the group consisting of alkanols, fatty acids, and alkylphen- 015.

3. A lubricant composition, as defined in claim 1, wherein said composition comprises a mineral-oil based composition.

4. A lubricant composition. as defined in claim I, wherein said composition comprises a synthetic-oil based composition.

5. A lubricant composition, as defined in claim 1, wherein said composition comprises an oil of lubricating viscosity in the range from about 45 SSU at 100F. to about 6000 SSU at 100F.

6. A lubricant composition, as defined in claim 1, wherein said composition comprises an oil of lubricating viscosity in the range from about 50 SSU at 210F. to about 250 SSU at 210F.

7. A lubricant composition, as defined in claim 1, wherein said composition comprises a grease.

8. A lubricant composition, as defined in claim I, wherein the sulfur in said mixture is present in an amount from about 0.0I to about l57c, by weight. of the total weight of the mixture.

9. A lubricant composition, as defined in claim I, wherein the sulfur in said mixture is present in an amount from about 0.5 to about 5%, by weight, of the total weight of the mixture.

10. A lubricant composition, as defined in claim I, wherein said mixture is present in an amount from about 0.I to about 30%, by weight, of the total weight of the composition.

11. A lubricant composition, as defined in claim I, wherein said mixture is present in an amount from about 3 to about l07r. by weight, of the total weight of the composition.

12. A mixture of an alkylene oxide polymer and sulfur.

13. A mixture, as defined in claim 12, wherein said alkylene oxide polymer comprises the reaction product of about I to about 30 moles of an alkylene oxide and about to 99 moles ofa member of the group consisting of alkanols, fatty acids, and alkylphenols.

14. A mixture, as defined in claim 12, wherein the sulfur is present in an amount from about 0.0l to about l5%, by weight, of the total weight of the mixture.

15. A mixture, as defined in claim 12, wherein the sulfur is present in an amount from about 0.5 to about 5%, by weight, of the mixture.

i l I

Claims (15)

1. A LUBRICANT COMPOSITION CONTAINING AN ANTI-WEAR AMOUNT OF A MIXTURE OF AN ALKYLENE OXIDE POLYMER AND SULFUR.

2. A lubricant composition, as defined in claim 1, wherein said alkylene oxide polymer comprises the reaction product of about 1 to about 30 moles of an alkylene oxide and about 70 to 99 moles of a member of the group consisting of alkanols, fatty acids, and alkylphenols.

3. A lubricant composition, as defined in claim 1, wherein said composition comprises a mineral-oil based composition.

4. A lubricant composition, as defined in claim 1, wherein said composition comprises a synthetic-oil based composition.

5. A lubricant composition, as defined in claim 1, wherein said composition comprises an oil of lubricating viscosity in the range from about 45 SSU at 100*F. to about 6000 SSU at 100*F.

6. A lubricant composition, as defined in claim 1, wherein said composition comprises an oil of lubricating viscosity in the range from about 50 SSU at 210*F. to about 250 SSU at 210*F.

7. A lubricant composition, as defined in claim 1, wherein said composition comprises a grease.

8. A lubricant composition, as defined in claim 1, wherein the sulfur in said mixture is present in an amount from about 0.01 to about 15%, by weight, of the total weight of the mixture.

9. A lubricant composition, as defined in claim 1, wherein the sulfur in said mixture is present in an amount from about 0.5 to about 5%, by weight, of the total weight of the mixture.

10. A lubricant composition, as defined in claim 1, wherein said mixture is present in an amount from about 0.1 to about 30%, by weight, of the total weight of the composition.

11. A lubricant composition, as defined in claim 1, wherein said mixture is present in an amount from about 3 to about 10%, by weight, of the total weight of the composition.

12. A mixture of an alkylene oxide polymer and sulfur.

13. A mixture, as defined in claim 12, wherein said alkylene oxide polymer comprises the reaction product of about 1 to about 30 moles of an alkylene oxide and about 70 to 99 moles of a member of the group consisting of alkanols, fatty acids, and alkylphenols.

14. A mixture, as defined in claim 12, wherein the sulfur is present in an amount from about 0.01 to about 15%, by weight, of the total weight of the mixture.

15. A mixture, as defined in claim 12, wherein the sulfur is present in an amount from about 0.5 to about 5%, by weight, of the mixture.