US3280030A - Lubricating composition - Google Patents

Description

United States Patent C) 3,28ll,(l30 LUBRICATING COMPGSITKON Edward L. Kay, Akron, Ghio, and Edwin C. Knowles and William R. Siegart, Poughkeepsie, and Frederic C. McCoy, Beacon, N.Y., assignors to Texaco Inc, New York, N.Y., a corporation of Delaware No Drawing. Filed Sept. 10, 1963, Ser. No. 307,782 7 Claims. (CL 252--49.7)

The present invention relates to a lubricating composition and, in particular, to mineral oil and synthetic ester base lubricating oils containing a complex or adduct of an inorganic halide and an amine to improve the load carrying properties of the lubricating composition.

New designs and improvements in machinery are continually raising the operating performance standards of lubricating compositions. In many instances, the pressures and temperatures to which the bearing surfaces of machinery operate under are higher than those which natural or synthetic lubricating oils can withstand. Instances where diffi-cult lubricating conditions are encountered occur in the lubrication of heavily loaded pinion and spur gears, gear trains, bearings, extrusion applications and the like. As a result, there is an increasing need for lubricating compositions having improved properties for these services.

A class of lubricating compositions has been discovered which possesses greatly improved properties for a variety of lubricating applications. These compositions are particularly notable for their improvement in load carrying properties but many of them also possess additional valuable features, such as corrosion resistance, oxidation resistance and stability. These compositions provide the answer to some heretofore difficult lubricating problems.

The present lubricating composition comprises a major proportion of a lubricating oil base, such as a mineral lubricating oil or a synthetic lubricating oil, and a minor amount of an oil-soluble adduct formed between a hydrocarbylarnine and an inorganic halide. More particularly, the additive of this invention is represented by the following formula:

wherein R is a hydrocarbyl radical having from 6 to 30 carbon atoms, R and R are hydrogen or a hydrocarbyl radical having from -1 to 30 carbon atoms, the sum of the carbon atoms in R, R and R being at least 12, y is an integer from 1 to 6, M is a polyvalent cation selected from the class consisting of aluminum, titanium,

tin, zinc, copper, cadmium, magnesium, mercury, zirconium, antimony, bismuth, manganese, and iron, X is a halogen selected from the group consisting of chloride, bromide and iodide ions and in the case of divalent tin and the cations having a valence of 3 to 4 the fluoride ion, and z is an integer from 2 to 4 equal to the valence of M.

The adducts of the invention are prepared by mixing one to six moles of a hydrocarbylamine defined above with a mole of the halide compound from the class set forth. Simple mixing of the reactants will generally produce the reaction. Optionally, the reaction can be effected in the presence of a solvent. Solvents which are suitableare those which can dissolve the inorganic compound. Particularly effective solvents include acetone, methanol and tetrahydrofu-ran. This reaction is usually exothermic and provision must generally be made for cooling the reaction mixture. Caution must be exercised to keep the reaction temperature below the decomposition temperature of both of the components of the reaction product which generally means conducting the reaction at a temice perature below about 200 C. The reaction generally goes to completion in a short reaction time.

Amines which can be employed for preparing the adduct of the invention are those amines having one or more hydrocarbyl radicals and in which the total number of carbon atoms in said radicals is at least 12. The requirement of 12 carbon atoms in the amine is critical to insure the oil solubility of the adduct. Adducts having less than 12 carbon atoms are generally not soluble in lubricating oils. The effective amines including primary, secondary and tertiary amines correspond to the formula:

wherein R is a hydrocarbyl radical having from 6 to 30 carbon atoms. R is generally a branched chain alkyl radical because of the ready availability of these materials. Preferably, R is a tertiary alkyl radical having from 12 to 30 carbon atoms. R may, however, be an aryl, aralkyl or alkaryl radical having the prescribed number of carbon atoms. R and R each represent hydrogen or a hydrocarbyl radical having from 1 to 30 carbon atoms of the same types defined for R. The sum of the carbon atoms in R, R and R as noted above is at least 12.

Examples of the effective amines include lau-rylamine, tricaprylylamine, d-i 2 ethylhexylamine, tridecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, tr-icosylamine, noncosylamine, nonylphenylamine, dodecylphenylami'ne, methyl dodecylamine, dimethyl dodecylamine, methyl octadecylamine and dimethyl octadecylamine. Particularly preferred amines are certain commercially available mixtures of tertiary alkyl primary amines. For example, a mixture of tertiary alkyl primary amines in which the alkyl radical comprises a mixture of alkyl groups having 11 to 14 carbon atoms is available under the name Primene 8 1-R. Another commercially available amine is the mixture of tertiary alkyl primary amines in which the alkyl radical comprises a mixture-of alkyl groups having 18 to 24 carbon atoms is available under the name of Primene JM-T.

Halides of metals and metalloids which can be employed to form the load carrying adducts of the invention include aluminum trichloride, aluminum trifluoride, titanium tetrachloride, titanium te-trafluoride, stannous chloride, stannous fluoride, stannic chloride, cupric chloride, cupric bromide, cadimum chloride, cadmium iodide, magnesium chloride, mercuric chloride, zirconium chloride, antimony chloride, antimony fluoride, bismuth chloride, manganese chloride, ferric chloride, zinc chloride, zinc bromide and zinc iodide. The preferred halides are those formed from titanium, tin, aluminum, antimony, zinc and copper.

Only specific halides as set forth above are effective for producing the adducts of the invent-ion. Examples of halides which do not form adducts include cuprous chloride, cupric fluoride, magnesium fluoride, manganous fluoride, antimony oxychloride, barium chloride, lithium chloride and calcium chloride.

An unexpected phenomenon is the discovery that the inorganic salt must have a substantial and apparently a critical degree of water solubility in order to form a complex with an amine of the type disclosed herein. The reason for the relationship between water solubility and complex formation is not fully understood. It has been determined, however, that the following critical conditions must he met in order to form a complex of the type disclosed:

(A) The metallic element of the salt must be capable of sharing the unpaired electron of the amine nitrogen.

(B) The salts must have a water solubility greater than 0.2 mole per' liter at a temperature in the range of 15- C.

8) Examples of inorganic salts and their behavior toward complex formation with a C primary amine (Primene JM-T) is given in Table I below:

TABLE .1

H2O Solubility, Mols Complex Formation Salt/l. of H20 With 021 Primary Amine 45 .3 (100 0.) Yes. 0.15 (95 C.) No. 14.2 (15 C.) Yes. 2.68 (18 C.) Yes. 30.0 (100 C.) Yes. 2.2 (100 C.) Yes. 0.00002 (43 C.) No.

The hydrocarbylamine and halide are reacted in the proportion of one to six moles of hydrocarbylamine to one mole of the halide compound with the preferred amount of the hydrocarbylamine being from one to four moles. Examples of adducts of the invention and the mole ratios of the components from which they were formed include the following:

Examples of other suitable adducts include:

Primene 8l-Rzstannic chloride (2:1), Tricaprylylaminezaluminum chloride (2:1), Tricaprylylamine:titanium tetrachloride (2:1), Di-2-ethylhexylamine:stannic chloride (2:1), Di-Z-ethylhexylarnine:titanium tetrachloride (2:1), and Di-2-ethylhexylamine:stannous fluoride (2:1).

The lubricating compositions of the invention are prepared by blending in a conventional way a minor amount of the oil-soluble, load-carrying hydrocarbylamine-halide adduct described hereinabove into a suitable lubricating oil base. Generally, the adduct is employed in an amount in the range of 0.05 to 10 percent by weight based on the Weight of the lubricating composition with the preferred proportions being from 0.1 to 3 weight percent.

The base lubricating oil can be a mineral lubricating oil or a synthetic lubricating oil. The mineral lubricating oil can be a predominantly parafiinic or naphthenic or it can be a mixture of both types of mineral oils. Generally, the mineral oil will be a refined oil of predominantly paraffinic nature having a viscosity in the range from 30 to 150 Saybo'lt Universal Seconds at 210 F.

Various types of synthetic lubricating oil bases can be employed in preparing the lubricants of the invention. Aliphatic ester, polyalkylene oxides, silcones, esters of phosphoric and salicyclic acid and the highly fluorine-substituted hydrocarbons can be employed. Examples of the aliphatic esters include di-(Z-ethylhexyl) sebacate, the dialkyl azelates, dialkyl suberates, and the dialkyl adipates such as di-hexyl azelate, di-(2-ethylhexyl) azelate, di- 3,5,5-trimethylhexyl glutarate, di-(2-ethylhexyl) adipate, tri-amyl tricarballyla-te, etc. The polyalkylene oxides inv 4 clude polypropylene oxide, polyisopropylene oxide diether, polyisopropylene oxide diesters, etc. The silicones include methyl silicone, methylphenyl silicone, and the silicates include tetraisooctyl silicate. The highly fluorinated hydrocarbons include fluorinated oil, perfluorohydrocarbons, etc.

Other effective synthetic lubricating oils include the neopentyl glycol esters such as, the neopentyl glycol propionates, neopentyl glycol butyrates and neopentyl glycol caprylates and the trimethylol alkanes such as trimethylol ethane, trimethylol propene, trimethylol pentane, trimethylol heptane and trimethylol dodecane and the like. Examples of the phosphate esters include tricresyl phosphate, trioctyl phosphate and tridecyl phosphate as well as mixed aryl and alkyl phosphates.

The load carrying ability of the lubricating compositions of the invention was determined by preparing mixtures of a mineral lubricating oil and a minor amount of a hydrocarbylamine-halide adduct of the invention and testing these lubricating compositions in the IAE Gear Test as a criterion of the =load carrying activity. The IAE Gear Test, which is described in British specification DERD 2487, is carried out in gears having a non-indexed type motion under a load of at least 40 pounds. The load carrying gears in this test were operated at a speed of 6,000 r.p.m. The effectiveness of the lubricants of the invention is shown in the Table II below:

TABLE II 11 The mineral oil employed was a solvent refined paraffin base distillate having an SUS viscosity at F. of about 130.

It is evident that the adduct-containing lubricating compositions were improved in their load carrying properties in the order of four to eight fold in comparison to the load carrying properties of the straight mineral oil.

The anti-scuffing and load carrying ability of a number of the lubricating compositions was determined in the well known Ryder Gear Test (Federal Test Method 6508). In this test, the lubricant is employed to lubricate two spur gears in a Pratt and Whitney Gear and Lubricating Tester (also called the Ryder Gear Tester). This tester was operated with a gear speed of 10,000 r.p.m. and with an oil inlet temperature of F. A loading pressure of 5.0 p.s.i. was applied during break-in. After ten minutes, the tester was shut down and the gear examined for the percentage of tooth area scuff on each tooth. The procedure was then repeated using high load pressures wit-h increments of 5 p.s.i. until 22.5 percent of the total tooth face area on the driving gear had been scuffed, the load applied in this run being considered the scuff load. The tooth load in pounds per inch of tooth width was then calculated.

The load carrying properties of some of the lubricating compositions was also determined by the Mean Hertz Lead Test. This test is run in a machine having four /2-inch diameter bearing balls which are driven under load while the balls are lubricated by the composition under test. This test is described in US. 2,600,058.

The lubricating compositions employed were prepared from two different base oils. Base Oil A was a mineral lubricating oil having an SUS viscosity at 210 F. of about 100. Base Oil B was a mineral lubricating oil hav- 6 ing an SUS viscosity at 210 F. of about 54. All the substantially improved extreme pressure, anti-wear and lubricant compositions contained 1 percent by weight of anti-scuff properties. They also exhibit good corrosion rethe indicated hydrocarbylamine-metal halide adduct. sistance, oxidation resistance and storage stability. These The results of this test are given in Table III below. valuble properties make the lubricants of the invention TABLE III 5 suitable for a broad range of lubricating applications. It is understood that the lubricating compositions of ff anti-Wear Properties in Ryder Gear and Mean the invention can contain numerous additives convenz Laud Tests tionally used to improve the properties of lubricating oils. Commonly employed additives are the methacryl- Ryder Mean 10 ates as V. I. improvers and pour point depressors, the Nature Adduct g gs Base on $55; 583': alkylphenols as oxidation inhibitors, alkaline earth metal p.p.ii salts of petroleum sulfonates or alkaryl sulfonates as detergents, metal di-al-kyl dithiop-hosphate corrosion inhibitors and silicone anti-foam fluids.

Obviously, many modifications and variations of the Primene JMT/TiF4 invention as hereinbefore set forth may be made without Pnmene JMT/sblls" departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are inn1caaryt nmmi/zeitjj:32: (heated 1n the appended clams- 1)l-Z-ethylhexylamine/ZnCl I Vie claim;

1. A lubricating composition comprising a major pro- The test results show that the lubricating compositions portion of a lubricating oil and 0:05 to 10 percent by of the invention have substantially improved anti-scuff, Weight of an oil-soluble adduct of a hydrocarbylamine anti-wear properties. The load carrying properties eX- and titanium tetrafiuoride having the formula: hibited are particularly valuable in lubricants for gas turbines. 4

In the following tests, the extreme ressure and wear properties and anti-scuff properties wire determined in wherein R a l'lydmcafrbyl radical having from 5 to lubricating compositions in which a synthetic base oil was K P atoms R and R are Selected from} the f P employed Base n C consisted of di 2 ethytht.xyl 1 30 slstlng of hydrogen and a hydrocarbyl radical having from acate plus sebacic acid which is commercially available 1 to zf a the Sum of carbfm atoms 111 as Plexol-201J The properties of these lubricating corn- R and R bemg at least n y 15 an Integer from positions were determined in the Mean Hertz Load Test 1 t t and the Navy Four Ball Wear Test A lubricating composition according to claim 1 in The Navy Four Ball Test is a test for determining the whlch Sald hydrocarbylamme 1S a laso P y alkylanti-wear properties of a lubricant. The test machine ammet comprises a system of 4 steel balls, 3 of which are in con- A lubncatmg {Omposltlon according to clalm 1 tact with each other in one plane in a fixed, triangular tammg 9 3 P F of l adductt position in a reservoir containing the oil sample and a A f f P? f amfordmg P f 1 In fourth ball above and in contact with the other three. In 40 which sald lumlcatmg mmeral lubricating carrying out the test, the upper ball is rotated while it is A lllbnca'tlflg F fi according to 1 i pressed against the lower three at any desired pressure Whlch 531d lubllcatmg a synthetfc lubricating by means of a suitable weight applied to a lever arm, and A hlbncamfi gompqsltwn acfiol'dlng 9 1 111 the diameters of the scars on the three lower balls are WhlCh Sald lubricating 011 is a dicarboxylic acid ester measured by the means of a low power microscope. 5 base t t t The average diameter, measured in two directions on A hlbrmatmg COmPQSItIOH accol'dlng to Claim 1 111 each of the three lower balls, is taken as a measure of whlch adduct 001151515 of ur-24 alkyl P y the anti-wear characteristics of the lubricant. The reamlmilltamum tetrafiuofidti in the mole ratio of 211 sults of these tests are given in Table IV below. reslmctlvely- TABLE IV References Cited by the Examiner Eflect of concentration an EP, wear and anti-scuff UNITED STATES PATENTS Fromm complex 2,181,915 12/1939 Rosen 252.495 X N F 2,278,851 4/1942 Hillman 25249.'7 X f 2,611,746 9/1952 Kipp 25249.6 oncmmtwnm') MHL 521L333 3,076,835 2/1963 Kay et al. 252-495 X Base on C n 16 1L8 FOREIGN PATENTS assis ant/ans: a to 505,433 8/1954 Canada Bilge on 0 Sins 3% Primene JM-T/SbFiiI 59 39 833,397 4/ 1960 Great Brltalll- The lubricating compositions containing the above- DANIEL WYMAN Primary Examiner described hydrocarbylamine-metal halide adducts have P. P. GARVIN, W. H. CANNON, Assistant Examiners.

Claims (1)

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR PROPORTION OF A LUBRICATINGG OIL AND 0.05 TO 10 PERCENT BY WEIGHT OF AN OIL-SOLUBLE ADDUCT OF A HYDROCARBYLAMINE AND TITANIUM TERAFLUORIDE HAVING THE FORMULA: