US2928789A

US2928789A - Mineral oil compositions

Info

Publication number: US2928789A
Application number: US428389A
Authority: US
Inventors: Thoburn P Sands
Original assignee: Monsanto Chemicals Ltd
Current assignee: Monsanto Chemicals Ltd; Monsanto Chemical Co
Priority date: 1954-05-07
Filing date: 1954-05-07
Publication date: 1960-03-15
Anticipated expiration: 1977-03-15

Description

trials MINERAL OIL COMPOSITIONS Thoburn P. Sands, Maplewood, Mo., assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application May 7, 1954 Serial No. 428,389

14 Claims. (Cl. 252-334) This invention relates to improvements in mineral oil lubricating compositions.

Many oil-soluble additives have been proposed for the purpose of imparting detergent-dispersant properties and oxidation inhibiting properties to mineral oil fractions employed as lubricating oils. In that no one substance satisfactorily imparts both oxidation inhibiting and detergent-dispersant properties to a mineral oil lubricating fraction various combinations of oil-soluble additives have been proposed and while some combinations are satisfactory the art has constantly sought improvements particularly with respect to the more efficient and more economical use of such additives.

Among the more effective additives imparting detergent-dispersant properties to mineral oil lubricating fractions are the oil-soluble metallo hydrocarbon sulfonates, particularly the oil-soluble metallo wax-alkylated aryl sulfonates. However, these detergents tend to increase the oxidation rate ofthe oil during use and their presence results in an increased concentration of acidic oxidation products in the oil. The increase in the amounts of these acidic oxidation products presents a serious corrosion problem particularly in internal combustion engines which employ alloy bearings. Antioxidants or oxidation inhibiting agents have been added to mineral oil lubricating compositions to prevent or inhibit the formation of mineral oil oxidation products and among the antioxidants proposed for use with the metallo hydrocarbon sulfonate detergent-dispersants are the expensive oil-soluble sul-' fit of their individual properties is not realized.

In accordance with this invention it has been found that the detergent-dispersant and oxidation characteristics of a mineral oil fraction of lubricating viscosity containing a minor proportion of a mixture of an oil-soluble phosphorizedand sulfurized-dicyclic terpene antioxidant and an'oil-soluble metallo hydrocarbon sulfonate detergent-dispersant is materially improved by incorporating therein a small amount of an oil-soluble sulfurized-monocyclic terpene. Furthermore a more stable and more economical mineral oil lubricating composition is obtained by the incorporation in a mineral oil containing a detergent-dispersant and an antioxidant of the aforesaid types .a small amount of a sulfurized-monocyclic terpene.

The amount of oil-soluble sulfurized-monocyclic terpene added to a mineral oil fraction containing an oilsoluble phosphorizedand sulfurized-dicyclic terpene antioxidant and an oil-soluble metallo hydrocarbon sulfonate detergent dspersant in order to provide a more stable, more efii ient and more economical lubricating composi- .tion will vary depending upon the circumstances, such as -lubr catmg compositions were prepared and evalnated for example the character of the mineral oil fraction, the concentrations and type of phosphorizedand sulfurizeddicyclic terpene antioxidant and metallo hydrocarbon sul-' fonate detergent-dispersant, the proposed use of the lubri eating composition, and the like; In general the concentrations by weight with respect to the oil base will be 0.l-10% of the metallo hydrocarbon sulfonate detergent-dispersant, ODS-3% of the phosphorizedand sulfurized-dicyclic terpene antioxidant and 0.05-2% of the sulfurized-monocyclic terpene, however, concentrations of the order of 0.45% by weight of the. sulfonate detergent-dispersant, 0.l-1% of the phosphorizedand sulfurized-dicyclic terpene, and 0.10.5% of the sulfurizedmonocyclic terpene with respect to the mineral oil fraction provide a highly efficient and economical lubricating oil composition which is satisfactory for most purposes. A particularly effective and economical lubricating composition is one containing predominantly a mineral oil fraction of lubricating viscosity and with respect to the oil base 0.2-0.4% by weight of an oilsoluble sulfurizedmonocyclic terpene, 0.2-0.4% by weight of an oil-soluble phosphorizedand sulfurized-dicyclic terpene, and 0.6-- 1.2% of an oil-soluble di-wax alkylated benzene sulfonate of an alkaline earth metal such as magnesium, calcium, strontium, or barium. For purposes of this invention magnesium is includedin the alkaline earth metal group.

In general a given quantity of a sulfurized monocyclic terpene of this invention upon its incorporation in a lubricating oil composition containing a phosphorizedand sulfurized-dicyclic terpene antioxidant and a metallo hydrocarbon sulfonate detergent-dispersant in effect is equivalent to the incorporation in the oil of approximately an equal weight of a phosphorizedand sulfurized-dicyclic terpene antioxidant and from approximately an equal weight to as much as four to five times its weight of a -:and sulfurized-dic'yclic terpene antioxidant and the metallo hydrocarbon sulfonate detergent-dispersant are necessary to provide a highly satisfactory and relatively inexpensive lubricating oil. To give a specific example the following lubricating mineral oil compositions were prepared and evaluated by the Coordinating Research Council L-4-'545 and L-1-545 tests and found to exhibit substantially the same oxidation stability and detergent-dispersant properties.

Lubricant Composition A B Parts by Parts by weight weight Mineral Oil of Lubricating Viscosity 88. 25 88, Basic Barium Salt of a Di-wax-alkylated 4 Bevene Sulfonic Acid (16.1% Barium; 1 3.87% Sulfu 1.63 0.65 Phosphorizedand Sulfurized-Pinene (7.7%

Pho phorus. 21.3% Sulfur) 0.52 v '0. 31 sulfurized-Dipeiteue (35% Sulfur) 0.22

By replacing the basic barium salt of the diwaxalkylated benzene sulfonic. acid in the above example with the corresponding basic magnesium salt substantially the same results are obtained. j r j,

As further illustrative of this invention the, following in a CRC Designation I. -4-545 (described on page 1395 Lubricant Composition D I Paris by Parts by weight weight Mineral Oil of Lubricating Viscosity. 98. 98. 52 Basic Barium Salt of a Di-wax-alkylat ed Benrene Sulfontc Acid (16.1% Barium; 3.87% Sulfur) 1. l9 ,0. 89 Phosphorizedand Sulfurized-Pinene (7.7%

Phosphorus, 21.3% Sulfur) 0. 63 0. 27 SulfurizedDipentene (35% Sulfur) 0; 32

Table I Lubricant Lubricant G D Bearing Corrosion (mgs. weight loss in metal per bearing) 81 69 Piston varnish rating (based on 8.9 9.1 Overall engine rating (based on 100) S6. 6 88. O

Lubricating Composition E F Parts by Paris by, 'weight weight Mineral Oil of Lubricating Viscosity 98.

Basic Barium Salt of a Di-wax-alkylated" 'Bo ene Sulfonic Acid (16.1% Barium;

3.87% Sulfur) .0. 84 'Phosphor'izedand Sulfurized-Pinene (7 .7%

, Phosphorus, 2i.3% Sulfur) Y O. 50 0.44 Sulfurized-Dipcntene (35% Sulfur) -4 0.13

Table II Lubricant E Lubricant F Time of Te t 240 hours 480 hours. No. l Groove (top ring). Moderate to heavy Moderate carbon 7 hard packed deposit.v carbon deposit. No. z Groove Moderate to heavy Very'light lacquer dark lacquer deposit over deposit plus some half of groove, carbon deposit. balance clean. No.13 Groove Moderate to heavy Stain on one half i dark lacquer of groove,

deposit over most balance clean. of groove. a

No. 4 Groove Light to moderate Clean.

dark lacquer deposit over most of groove.

Piston Skirt Trace of amber D0.

lacquer deposit on front side.

The oil-soluble sulfurized-monocyclic terpene hydrocarbons of this invention may be prepared by any of the well known methods for sulfurizing unsaturated hydro "'monocyclic terpene additives are the sulfurized-dipentenes "containing 3040% sulfur by weight, however, any

sulfurizecl monocyclic terpene containing about 24-60% by weight is satisfactory. Sulfurized-monocyclic terp'enes containing as little as sulfur by weight are also contemplated.

The oil-soluble sulfurizedand phosphorized-dicyclic terpene hydrocarbon antioxidants ofthis invention are ithoseobtainedby reacting a dicyclic terpene hydrocarbon atoms.

suchas pinene, camphene, fenchene and similar terpencs possessing one double bond in the molecule and comprising two ring systems, with a phosphorus sufilde at a reaction temperature of about 100-160 C. While any phosphorus sulfide such as P 8 P 8 P 8 P 8 P 5 andthe like, may be employed in the preparation of said reaction products, the preferred reaction products are those obtained employing phosphorus pentasulfide. While the proportions of these reactants will vary depending upon the oil-soluble and oil-improvement properties desired the preferred product is that obtained by the reaction of approximately one molecular-proportion of a phosphorus sulfide, such as P S ,with approximately four molecular proportions of a dicyclic terpene, such as pinene, at a reaction temperature of lO0-160 C.

The preferred oil-soluble metallo hydrocarbon sulfonate detergent-dispersants of this invention are those obtained by sulfonatingwax-alkylated aromatic hydrocarbons and forming neutral or basic metal salts thereof. This class may be represented by the general formula where n is a whole number from 1 to 4, preferably 2,

where R is an aromatic hydrocarbon radical such as phenyl, tolyl, xylyl, cumyl, naphthyl, biphenyl, etc. where M is a bivalent metal such as zinc, the alkaline earth metals such as magnesium, calcium, strontium, barium, and the like, where X is SO R-(wax),, or preferably a hydroxyl group. The Wax substituent or substituents of the preferred detergent-dispersant of this invention consists of carbon and hydrocarbon as distinguished from ester waxes. The hydrocarbon wax substitucnt contains at least 18 carbon atoms in the lowest carbon chain and is derived from hydrocarbon waxes having melting points varying between about 90 F. and about 180 F. The preferred wax substituents are those known in the art as paraflin waxes which contain at least 20 carbon atoms and usually not more than 30 and which have melting points varying from 90 to 140 F. Other hydrocarbon wax substituents are the cerese waxes Which-have, melting points as high as 180 F. and are derived from petroleum. Other oil-soluble metallo alkylated aryl sulfonate detergent-dispersants are also contemplated for example, those aryl sulfonates containing alkyl groups possessing not less than eight carbon Other typical oil-soluble hydrocarbon sulfonate detergent-dispersants are those obtained by sulfonating paraffins, naphthenes the various parafiinic, naphthenic and aromatic petroleum fractions and the like, and forming the neutral metal or basic metal salts thereof. As exemplary of the preferred detergent-dispersants are the basic magnesium, neutral magnesium, basic calcium, neutral calcium, strontium, basic barium, and neutral barium salts of di-wax-alkylated benzene sulfonic acids. Other detergent-dispersants within the scope of this in oil sulfonate.

While the inventionjhas been described with respect to certain preferred embodiments it is not so limited in that various modifications may be made which are obvious to those skilled in the art as for example the inclusion of stabilization agents, pour point depressants, extreme pressure lubrication improving agents, viscosity improving agents, and the like, without departing from the spirit or scope of the invention.

This application is a continuation-in-part of co-pending application Serial No. 208,054, filed January 26, 1951, now abandoned.

What is claimed is:

l. .A lubricating composition comprising a mineral oil and with respect to the mineral oil about 0.140% by weight of an oil-soluble metallo'hydroearbon sulfonate detergent, about 0.0$-3% by weight of an oil-soluble phosphorizedand sulfurized-dicyclic terpene, and about 0.05-2% by weight of an oil-soluble sulfurized-monocyclic terpene.

2. A lubricating composition comprising a mineral oil fraction of lubricating viscosity and with respect to the mineral oil fraction about 01-10% by weight of an oilsoluble metallo wax-alkylated aromatic hydrocarbon sulfonate detergent, about 0.05-3% by weight of an oil-soluble phosphorizedand sulfurized-dicyclic terpene obtained by reacting a phosphorus sulfide with a dicyclic terpene, and about 0.05-2% by Weight of an oil-soluble sulfurized-monocyclic terpene containing 24-50% sulfur by weight.

3. A lubricating composition comprising predominantly a mineral oil fraction of lubricating viscosity and with respect to the mineral oil fraction about 0.1% by weight of an oil-soluble basic barium wax-alkylated aryl sulfonate detergent of the general formula where n is a whole number from l-3 inclusive and where R is a benzenoid hydrocarbon radical containing but one uncondensed benzene nucleus, about 0.05-3% by weight of a phosphorizedand sulfurized-dicyclic terpene obtained by reacting a phosphorus sulfide with a dicyclic terpene at about 100l60 C., and about 0.052% by weight of a sulfurized-monocyclic terpene containing 30- 40% by weight sulfur.

4. A lubricating composition comprising predominantly a mineral oil fraction of lubricating viscosity and with respect to the mineral oil fraction about 0.1-10% by weight of an oil-soluble metallo wax-alkylated aryl sulfonate detergent of the general formula Where n is a whole number from l-4, where R is an aromatic hydrocarbon radical, where M is a divalent metal, and where X is selected from the group consisting of a hydroxyl group and (wax),,-RSO about 0.05- 3% by weight of a phosphorizedand sulfurized-dicyclic terpene obtained by reacting about one molecular proportion of a phosphorus sulfide with about four molecular proportions of a dicyclic terpene at about 100-l60 C., and about ODS-2% by weight of a sulfurized-monocyclic terpene containing 30-40% by weight sulfur.

5. A lubricating composition comprising predominant- 1y a mineral oil fraction of. lubricating viscosity and with respect to the mineral oil fraction about 0.1-10% by weight of an oil-soluble metallo wax-alkylated aryl sulfonate detergent of the general formula (wax) SOs-M-OH where M is an alkaline earth metal, about 0.053% by weight of a phosphorizedand sulfurized-pinene obtained by reacting substantially one molecular proportion of phosphorus pentasulfide with substantially four molecular proportions of pinene at -l60 C., and about 0.05- 2% by weight of a sulfurized-dipentene containing 30- 40% by weight sulfur.

7. A lubricating composition comprising predominantly a mineral oil fraction of lubricating viscosity and with respect to the mineral oil fraction about 0.4-5% by weight of an oil-soluble metallo wax-alkylated aryl sulfonate detergent of the general formula (wax) 3 S 0 3 M where M is an alkaline earth metal, about 0.1-1% by weight of a phosphorizedand sulfurized-pinene obtained by reacting substantially one molecular proportion of phosphorus pentasulfide with substantially four molecular proportions of pinene at l00-l60 C., and about 0.1- 0.5% by weight of a sulfurized-dipentene containing 30- 40% by weight sulfur.

8. A' lubricating composition comprising predominantly a mineral oil fraction of lubricating viscosity and with respect to the mineral oil fraction about 0.45% by weight of an oil-soluble metallo wax-alkylated aryl sulfonate detergent of the general formula (wa SOs-M-OH where M is an alkaline earth metal, about 0.1-1% by weight of a phosphorizedand sulfurized-pinene obtained by reacting substantially one molecular proportion of phosphorus pentasulfide with substantially four molecular proportions of pinene at 100-l60 C., and about 0.1- 05% by weight of a sulfurized-dipentene containing 30- 40% by weight sulfur.

9. A lubricating composition comprising predominantly a mineral oil fraction of lubricating viscosity and with respect to the mineral oil fraction about 0.6-1.2% by weight of an oil-soluble metallo wax -alkylated aryl sulfonate detergent of the general formula (wax) 2 S0 M where M is an alkaline earth metal, about 0.2-0.4% by Weight of a phosphorizedand sulfurized-pinene obtained by reacting substantially one molecular proportion of phosphorus pentasulfide with substantially four molecular proportions of pinene at 100-160 C., and about 0.2- 0.4% by weight of a sulfurized-dipentene containing about 35% by weight sulfur.

10. A lubricating composition comprising predominantly a mineral oil fraction of lubricating viscosity and with respect to the mineral oil fraction about 0.6-1.2% by weight of an oil-soluble metallo wax-alkylated aryl sulfonate detergent of the general formula where M is an alkaline earth metal, about 0.2-0.4% by weight of a phosphorizedand sulfurized-pinene obtained by reacting substantially one molecular proportion of phosphorus pentasulfide with substantially four moleculat proportions of pinene at l-l60 C., and about 02-04% by weight of a sulfuriZed-dipentene containing about 35% by weight sulfur.

11. A lubricating composition comprising predominantly a mineral oil fraction of lubricating viscosity and with respect to the mineral oil fraction about 06-12% by weight of an oil-soluble barium wax-alkylated aryl sulfonateof the general formula (wax) 2 S O 3 Ba about 0.2-0.4% by weight of a phosphorizedand sulfurized-pinene obtained by reacting substantially one molecular proportion of phosphorus pentasulfide with substantially four molecular proportions of pinene at 100-l60 C., and about 02-04% by weight of a sulfurized-dipentene containing about 35% by weight sulfur.

12. A lubricating composition comprising predominantly a mineral oil fraction of lubricating viscosity and with respect to the mineral oil fraction about 06-12% by weight of an oil-soluble barium wax-alkylated aryl sulfonate of the general formula about (ll-6.4% by weight of a phosphorizedand sulfurized-pinene obtained by reacting substantially one molecular proportion of phosphorus pentasulfide with substantially four molecular proportions of pinene at l0O-l60 C., and about 02-04% by weight of a sulfurized-dipentene containing about 35% by weight sulfur.

13. A lubricating composition comprising predominantly a mineral oil fraction of lubricating viscosity and with respect to the mineral oil fraction about (lo-1.2% I

by weight of an oil-soluble magnesium wax-alkylated aryl sulfonate of the general formula where the wax substituent is derived from a parafiin wax containing 20-30 carbon atoms having a melting point of -140 F., about 0.20.4% by weight of a phosphorizedand sulfuriZed-pinene obtained by reacting substantially one molecular proportion of phosphorus pentasulfide with substantially four molecular proportions of pinene at -160 C., and about 02-04% by weight of a snfurized-dipentene containing about 35% by weight sulfur.

References Cited in the file of this patent 1 UNITED STATES PATENTS 2,417,305 Knowles Mar. 11, 1947 2,493,216 Berger Ian. 3, 1950 2,643,248 Brennan June 23, 1953 2,721,862 Brennan Oct. 25, 1955

Claims

1. A LUBRICATING COMPOSITION COMPRISING A MINERAL OIL AND WITH RESPECT TO THE MINERAL OIL ABUT 0.1-10% BY WEIGHT OF AN OIL-SOLUBLE METALLO HYDROCARBON SULFONATE DETERGENT, ABOUT 0.05-3% BY WEIGHT OF AN OIL-SOLUBLE PHOSPHORIZED- AND SULFURIZED-DICYCLIC TERPENE, AND ABOUT 0.05-2% BY WEIGHT OF AN OIL-SOLUBLE SULFURIZED-MONOCYCLIC TERPENE.