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Publication numberUS3890363 A
Publication typeGrant
Publication dateJun 17, 1975
Filing dateMay 24, 1974
Priority dateApr 6, 1973
Also published asUS3833496
Publication numberUS 3890363 A, US 3890363A, US-A-3890363, US3890363 A, US3890363A
InventorsRobert E Malec
Original AssigneeEthyl Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Oil additive
US 3890363 A
Abstract
Compounds having the formula:
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Description  (OCR text may contain errors)

United States Patent [1 1 Malec y 1 OIL ADDlTlVE Inventor: Robert E. Malec, Birmingham,

Mich.

Assignee: Ethyl Corporation, Richmond, Va.

Filed: May 24, 1974 Appl. No.: 473,129

Related US. Application Data u.s. Cl 260/455 A; 252/34; 252/475 Int. Cl. C07C 5 0 C07C 155 0 c07c 155/08 Field of Search 260/455 A References Cited UNITED STATES PATENTS 7/1958 Andersen et al "260/455 A 4/1965 Ross et'al. 260/455 A Primary Examiner-Lewis Gotts Assistant Examiner-D. R. Phillips Attorney, Agent, or FirmDonald L. Johnson; Robert A. Linn; Joseph D. Odenweller Division of Ser. No. 348,625, April 6, 1973, Pat. No.

[1-11 3,890,363 June 17, 1975 7 ABSTRACT Compounds having the formula;

5 ll R' -:m' I c -:-c!ivR3 R4 wherein R'is selected from the group consisting of aliphatic hydrocarbon radicals containing about 8-100 carbon atoms, and hydrocarbylaminohydrocarbyl radicals having the formula:

wherein R is an aliphatic hydrocarbon radical containing about 8-100 carbon atoms, R" is selected antirust additives in lubricating oils and greases.

6 Claims, No Drawings OIL ADDITIVE This application is a division of application Ser. No. 348,625, filed April 6, 1973, now US. Pat. No. 3,833,496.

BACKGROUND Additives are conventionally added to lubricating oil and grease to improve their properties. Antiwear additives used in the past include compounds such as zinc dialkyldithiophosphates, sulfurized sperm oil, and the like. Antirust protection can be provided by compounds such as overbased calcium sulfonates. Long chain amines such as polybutenyl ethylenediamine have been used to improve dispersancy of lubricating oils.

SUMMARY OF THE INVENTION According to the present invention, lubricating oils and greases having improved antiwear and antirust properties are provided by including in the lubricating oil composition certain 3-mercaptoalkanoic acid, [(alkylamino)alkyl] dithiocarbamates such as 3- mercaptobutyric acid, [3(oleylamino)-propyl] dithiocarbamate.

DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of the invention is an antiwear-antirust additive for lubricating oils and greases having the formula:

wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing about 8-100 carbon atoms, and hydrocarbylaminohydrocarbyl radicals having the formula:

wherein R is an aliphatic hydrocarbon radical containing about 8-100 carbon atoms, R"" is selected from the group consisting of hydrogen and C alkyls and R is a divalent aliphatic hydrocarbon radical containing about 2-10 carbon atoms, R and R are selected from the group consisting of hydrogen and alkyl radicals containing about 14 carbon atoms, R" is selected from the group consisting of hydrogen and C alkyls and R' is selected from the group consisting of hydrogen and salt cations. Useful salt cations include the cations of the alkaline earth metals such as calcium, magnesium, strontium, and barium; ammonium ions formed from ammonia; alkyl and alkenyl amines such as methylamine, dimethylamine, trimethylamine, triethylamine, tributylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, stearylamine, oleylamine, palmylamine, laurylamine, eicosylamine, eicosenylamine, and the like; and other metal cations such as zinc, aluminum, nickel, manganese, iron, and the like.

Representative examples of the above additives in clude:

2 3-mercaptopropionic acid, n-octyldithiocarbamate 3-mercaptobutyric acid, stearyldithiocarbamate calcium S-mercaptobutyrate, oleyldithiocarbamate zinc 3-mercaptopropionate, palmyldithiocarbamate trimethylammonium 3-mercaptohexanoate, C

polybutenyl dithiocarbamate manganese 3-mercaptobutyrate, stearyldithiocarbamate barium 3-mercaptoheptanoate, eicosyldithiocarbamate magnesium 3-mercaptobutyrate, eicosenyldithiocarbamate triethanolammonium 3-mercaptobutyrate, oleyldithiocarbamate A most preferred embodiment of this invention is an antiwear-antirust additive for lubricating oils and greases, said additive having the formula:

wherein R is an aliphatic hydrocarbon radical containing from about 8-100 carbon atoms, R is a divalent aliphatic hydrocarbon radical containing from 2 to about 10 carbon atoms, and R and R are selected from tl" group consisting of hydrogen and alkyl radicals containing l to about 4 carbon atoms. Since the compounds contain both a basic amine functional group and a carboxylic acid they can exist in the form of a zwitterion and are shown in that form in Formula [1. Representative examples of such additives include: 3-mercaptopropionic acid, [2(9- eicosenylamino)ethyl]dithiocarbamate 3-mercapto-2-methylbutyric acid, [6(octylamino)hexyl]dithioca'rbamate 3-mercaptoheptanoic cyl]dithiocarbamate 3-mercapto-2-methylhexanoic acid,

hexylbutylamino) butyl] dithiocarbamate 3-mercapto-2-butylheptanoic acid, [3(pentacontenylamino) propyl] dithiocarbamate B-mercaptobutyric acid,

tylamino)ethyl]dithiocarbamate S-mercaptopropionic acid, [3(octacontylamino)propyl]dithiocarbamate 3-mercaptohexanoic acid,

polybutenylamino) propyl] dithiocarbamate 3-mercaptobutyric acid, [3(C -p0lypropenylamino) propyl] dithiocarbamate 3-mercaptooctanoic acid, [3(dodecenylamino)bu- [2(hexacontyl]dithiocarbamate 3-mercaptopropionic acid, [3(tetracosylamino)propyl]dithiocarbamate 3-mercaptobutyric acid, [6(stearylamino)- hexyl]dithiocarbamate 3-mercaptopentanoic acid, [4(palmylamino)butyl]dithiocarbamate 3-mercaptobutyric acid, [3( 2- nonacontenylamino )propyl]dithiocarbamate A preferred class of additives are those of Formula I] wherein R contains about 8-22 carbon atoms, R is the trimethylene radical (CH R is the methyl radiacid, [l0(laurylamino)decal, and R is hydrogen. Examples of these compounds are:

3-mercaptobutyric acid, [3(oleylamino )propyl]dithiocarbamate 3-mercaptobutyric acid, [3(steary1amino)propyl]dithiocarbamate B-mercaptobutyric acid, [3(palmylamino)propyl ]dithiocarbamate The additives are readily prepared by reacting an aliphatic hydrocarbylaminohydrocarbylamine with carbon disulfide to form the corresponding hydrocarbylaminohydrocarbyl dithiocarbamic acid and reacting this with an appropriate alpha-unsaturated aliphatic carboxylic acid such as acrylic acid, crotonic acid, a-methyl crotonic acid, a,B-diethyl acrylic acid, B-butyl acrylic acid, a-butyl acrylic acid, and the like (N. Kreutzkamp et al, Arch. Pharm. 304, p. 477-481, July 1971 l The aliphatic hydrocarbylaminohydrocarbylamines can be prepared by reacting an aliphatic hydrocarbyl chloride with an aliphatic diamine. For example, reaction of oleyl chloride with 1,3-propanediamine yields oleylaminopropylamine. Likewise, reaction of lauryl chloride with 1,6-hexanediamine forms laurylaminohyexylamine. Similarly, reaction of C -polybutenyl chloride with ethylenediamine forms C polybutenylaminoethylamine. The polyolefin chlorides are readily formed by reacting a polyolefin (e.g., polypropylene, polybutene, and the like) with chlorine.

The following example illustrates the manner in which the additives can be prepared.

EXAMPLE 1 To a solution of 175 grams of N-oleyl-l,3- propanediamine and 175 grams of isopropyl'alcohol was added a solution of 40 grams of carbon disulfide and 40 grams of isopropyl alcohol over a one hour period at 0lOC. The unreacted carbon disulfide was distilled off and 50 grams each of crotonic acid, isopropyl alcohol and methanol was added. The mixture was stirred at 010C for 2 hours and then allowed to warm to room temperature. The product was diluted with hexane and washed with water, following which volatile material was distilled out under vacuum to yield 184 grams of a low melting solid.

EXAMPLE 2 A portion of the product from Example 1 was diluted with hexane, filtered, water washed, and then the hexane distilled out. The resultant product was diluted with neutral mineral oil to obtain a 67 weight percent active concentrate. This was diluted with hexane and washed with aqueous ammonia. Powdered solid carbon dioxide was added and stirred into the mixture. The mixture was then water washed, following which hexane was distilled out, leaving a viscous yellow liquid concentrate.

Modification of the above procedure by substitution of different starting hydrocarbylaminohydrocarbylamines and different alpha-unsaturated aliphatic carboxylic acids will lead to the other additives within the scope of this invention.

The additives are useful in lubricating oils and greases including both mineral and synthetic. Synthetic oils include polyolefin oils (e.g., polybutene oil, decene oligomer, and the like), synthetic esters (e.g., dinonyl sebacate, trioctanoic acid ester of trimethylolpropane,

and the like), polyglycol oils, and the like. Greases are madefrom these'oils by adding a thickening agent such as sodium, calcium, lithium, or aluminum salts of fatty acids such as stearic acid. The oils and greases are prepared by blending an antiwear and antirust amount of the additive into the oil or grease. A useful concentration is from about O.l to 5 weight percent. The additives may be added in the form of a concentrate such as the mineral oil diluted concentrate described in Example 2.

Other additives may be included in the oil or grease compositions. These include such additives as zinc dialkyldithiophosphates, barium phenates, calcium phenates, calcium aryl sulfonates, magnesium aryl sulfonates, overbased calcium aryl sulfonates, barium polybutenyl phosphonates; antioxidants such as 4,4- methylenebis(2,6-di-tert-butylphenol), a-dimethylamino-2,6-di-tert-butyl-p-cresol; dispersants such as polybutenyl succinimides of ethylenepolyamines, polybutenyl ethylenediamines, viscosity index improvers such as polybutenes, ethylene-propylene copolymers, polylauryl methacrylates, and the like.

Tests have been carried out to demonstrate the antiwear and antirust properties of the additives. The first is known as the four-ball cam and tappet test. In this test, three steel balls are placed in a triangular manner in a circular retainer containing the test oil. A fourth ball is placed on top of these three to form a triangular pyramid. A 50 Kg load is placed on the top ball and it is rotated at 1800 rpm. for one hour with the oil heated to l 10C. This test has previously been shown to correlate well with the cam and tappet wear of an internal combustion engine. Criteria is the average scar diameter formed on the three bottom balls. A scar diameter of 1 mm or less is considered satisfactory.

The test was carried out on a non-additive neutral oil and on triplicate samples containing 1 weight percent of the additive of Example 1 3-mercaptobutyric acid, [3(oleylamino)propyl] dithiocarbamate. The results obtained were as follows.

TABLE 1 Additive Average scar diameter (mm) None 2.3 Example I (1%) '0.92, 0.99, 0.89

TABLE 2 Additive Results None both fail Example 2 (1%) all pass These results demonstrate the excellent antiwear and antirust properties of the present additives.

I claim: 1. An antiwear-antirust additive for lubricating oils and greases, said additive having the formula:

c v u wherein R' is selected from the group consisting of aliphatic hydrocarbon radicals containing about 8-100 carbon atoms, and hydrocarbylaminohydrocarbyl radicals having the formula:

2. An antiwear-antirust additive of claim 1, said additive having the formula:

wherein R is an aliphatic hydrocarbon radical containing from about 8-100 carbon atoms, R is a divalent aliphatic hydrocarbon radical containing from 2 to about 10 carbon atoms, and R and R are selected from the group consisting of hydrogen and alkyl radicals containing 1 to about 4 carbon atoms.

3. An additive of claim 2 wherein R contains about 8-22 carbon atoms, R is the trimethylene radical, R is the methyl radical, and R is hydrogen.

4. An additive of claim 3 wherein R is the oleyl radical.

5. An additive of claim 3 wherein R is the stearyl radical.

6. An additive of claim 3 wherein R is the palmyl radical.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2841530 *May 18, 1955Jul 1, 1958Ameringen Haebler Inc VanHair waving compositions containing secondary amino aliphatic alcohol dithiocarbamates
US3180791 *Jul 2, 1963Apr 27, 1965Montedison SpaMethod of controlling fungi with organic sulfur ester compounds
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4360438 *Jun 6, 1980Nov 23, 1982R. T. Vanderbilt Company, Inc.Organomolybdenum based additives and lubricating compositions containing same
US4609480 *Jul 31, 1985Sep 2, 1986Idemitsu Kosan Company LimitedLubricant composition for improving fatigue life
US4758362 *Mar 18, 1986Jul 19, 1988The Lubrizol CorporationCarbamate additives for low phosphorus or phosphorus free lubricating compositions
US4859352 *Feb 29, 1988Aug 22, 1989Amoco CorporationBlend of lithium soap, synthetic oil, and adjuvants
US4997969 *Dec 12, 1988Mar 5, 1991The Lubrizol CorporationDithiocarbamates
US5674820 *Sep 5, 1996Oct 7, 1997The Lubrizol CorporationAdditive compositions for lubricants and functional fluids
US5693598 *Sep 3, 1996Dec 2, 1997The Lubrizol CorporationLow-viscosity lubricating oil and functional fluid compositions
US5705458 *Oct 24, 1996Jan 6, 1998The Lubrizol CorporationAdditive compositions for lubricants and functional fluids
US5726132 *Feb 28, 1997Mar 10, 1998The Lubrizol CorporationLubricants
US5759965 *Oct 17, 1996Jun 2, 1998The Lubrizol CorporationAntiwear enhancing composition for lubricants and functional fluids
US5843873 *Jun 24, 1997Dec 1, 1998The Lubrizol CorporationLubricants and fluids containing thiocarbamates and phosphorus
US5902776 *May 7, 1998May 11, 1999The Lubrizol CorporationOrganic phosphorus-containing salt and a thiocarbamate which are useful in providing enhanced antiwear properties to lubricants and functional fluids
US5913112 *Mar 11, 1994Jun 15, 1999Semiconductor Energy Laboratory Co., Ltd.Method of manufacturing an insulated gate field effect semiconductor device having an offset region and/or lightly doped region
US8349215 *Dec 10, 2008Jan 8, 2013Clariant Finance (Bvi) LimitedCorrosion inhibitors having increased biological degradability and minimized toxicity
US20100283010 *Dec 10, 2008Nov 11, 2010Clariant Finance (Bvi) LimitedCorrosion Inhibitors Having Increased Biological Degradability And Minimized Toxicity