US3189544A - Non-ash-containing lubricating oil composition - Google Patents

Description

United States Patent Ofiice 3,l89,544 Patented June 15, 1965 3,189,544 NQN-ASH-QQNTAWING LUBREQATING OIL CGIVTFOSTTION Hyman Battier, Florissant, Mo and Roland F. Bergstrom, Martinez, Caiiil, assignors to Shell Gil Company,

New York, N.Y., a corporation of Delaware No Drawing. Filed Dec. 19, 1962, Ser. No. 245,682 13 Qlaims. (Cl. 25233) This invention relates to new and improved lubricating oil compositions possessing beneficial multifunctional properties. More particularly the invention relates to highly detergent nonash forming mineral lubricating oil compositions which are wear resistant and non-corrosive.

It is known that lubricating oils containing certain metallic salts or soaps such as metal sulfonates possess good dispersing and detergent properties. Such lubricants, however, tend to form metallic deposits on engine. Recent trends in this field have been to use of non-ash forming basic and essentially neutral polymeric nitrogencontaining dispersants such as copolymers of polymerizable amines or amides with long-chain acrylate esters of high molecular weight. These non-ash forming nitrogen-containing compounds are excellent detergents but under engine operating conditions they lack stability and corrosion and Wear inhibiting properties. Attempts to improve these polymeric detergent materials either by modification or use of auxiliary additives has met wi little success. In most cases the auxiliary additives which are promising stabilizers and wear inhibitors are metal-containing compounds such as metal sulfonates or metal carboxylates and these are to be avoided for reasons stated.

it is an object of the present invention to provide an improved non-ash forming lubricating oil composition. It is another object of the invention to provide an improved detergent lubricant possessing good stability and antiwear properties. Still another object of the invention is to provide a corrosion resistant non-ash containing or forming lubricating oil composition. Other objects will become apparent during the following description of the invention.

Now in accordance with the present invention, it has been found that stability, sludge, wear and corrosion inhibiting properties can be imparted to lubricating oils by incorporating therein a small amount of an oilsoluble oragnic sulfonic acid salt of an amino-imide of a long-chain monosubstituted polymeric hydrocarbyl succinic anhydride. By long-chain is meant an olefinic polymer straight or branch chain and derived from olefins of from 2 to 8 carbon atoms such as ethylene, propylene, l-butene, isobutene, l-hexene, styrene, ct-methyl-styrene and copolymers thereof, of from 20 to 500 carbon atoms and a molecular weight of 300 to 5000, preferably from 800 to 1500 as determined by the light scattering method.

The olefinic polymer present as an oil-solubilizing substituent and detergent aid of the polymeric nitrogencontaining amino-inside sulfonic acid salts of the present invention may be prepared by any known means provided it is within the molecular weight range indicated above. Examples of such polymers include polyethylene, polypropylene, polybutene, polyisobutylene, copolymer of ethylene/propylene, copolymer of ethylene/isobutylene, copolymer of ethylene/a-methylstyrene and the like. Monoalkylation of maleic anhydride with the above type olefinic polymers may also be made by conventional means known in the art, preferably in the absence of a. catalyst and at temperatures ranging from about 300 F. to 600 F, preferably between 350 F. and 450 F. The mole ratio of the polyolefin to maleic anhydride may vary from 1:1 to 1:10, preferably from 1:1 to 1:5; respectively.

The amines used to form the succinimide which constitutes the cationic portion of the sulfonate salts of the present invention include alkylene polyamines such as ethylene diamine, diethylene triamine, triethylene tetramine, l-methyl ethylene diamine, l-ethyl ethylene diamine, propylene diamine, butylene diamine, trimethyl trimethylene diamine, tetramethylene diamine, diaminopentane or pentamethylene diamine, diaminohexane, hexamethylene diamine, heptarnethylene diamine, diaminooctane, decamethylene diarnine, and the higher homologues of up to 19 carbon atoms; phenylene diamine, the alkylated phenylene diamines having nuclear substituents such as methyl, ethyl, propyl, butyl, etc., naphthalene diamine, and the alkylated naphthalene diames; N,N'dimethyl ethylene diamine, N,N'-(diethyl)ethylene diamine, N,N-(dipropyl)ethy1ene diamine, N,N-(2-hydroxypropyD-ethylene diamine, N,N-(diethyl)propylene diarnine, N,N-(dipropyl)propylene diamine, N,N'-(dimethyl)butylene diamine, N,N-(diethyl)butylene diamine; penta-(l-methylpropylene)hexamine; tetrabutylene pentamine; hexa-(1,l-dimethylethylene)heptamine; di (1-methylbutylene)triarnine; pentaamylenehexamine; tri-( 1,2,2-trimethylethylene)tetramine; di-( l-methylamylene)tramine; tetra (1,3 dimethylpropylene)pentamine; penta (1,5-dirnethylamylene)hexamine; di-(l-methyl-L ethylbutylene)triamine; penta (1,2-dimethyl-1-isopropylethylene)hexamine; tetraoctylenepentamine and the like.

The polyalkylenepolyamines can be prepared by several methods well known to the art. One well accepted method comprises reacting ammonia with an alkyl, or substituted alkyl dihalide. For example, tetraethylenepentamine has been prepared by reacting ammonia with ethylene bromide. The preferred polyamines are the ethylene amines such as ethylene diamine, diethylene triamine, triethylenc tetramine, tetraethylene pentamine, N-dimethyl aminopropylamine, N-dimethylaminobutylamine, N-diethylaminopropylamine, methylpropylarnino amylamine.

In forming the cationic portion of the salt the mole ratio of the monopolyolefinic succinic anhydride and polyamine and the reaction temperature must be carefully controlled to obtain desired end product. The mole ratio of the polyamine to the olefinio substituted succinic anhydride can vary from 0.1:1 to 1:1 respectively. The reaction temperature may vary from 220 F. to 500 F, preferably from 300 F. to 450 F.

The cationic portion of the salts of this invention are illustrated by the following examples.

EXAMPLE I 250 gms. of polyisobutylene having a molecular weight of 615 and bromine number of 21 was heated to 212 F. and 30 grns. of maleic anhydride was added slowly over a period of 30 minutes. The reactants were heated to 390 F. to 400 F. and maintained at this temperature for four hours and then heated to 440 F. and maintained at this temperature for 16 hours. On cooling, the reactants were dissolved in 1.5 liters of petroleum spirit (GO- C. RP.) and filtered. 19 gms. of tetraethylene pentamine was added to the petroleum spirit solution. The petroleum spirit was distilled off and re placed by 1 liter of toluene which was also distilled oft to azeotropically remove Water, and the residue was heated to 390 F. to 400 F. and maintained at this temperature for three hours.

(1 mole) of maleic anhydride was heated at 410 F. in a nitrogen atmosphere with agitation for period of 24 hours.

The reaction mixture was cooled to 150 F. and 760 cc.

of hexane added; after which the mixture was filtered under vacuum. After vacuum'distillation to remove the hexane from the filtrate, the product was maintained at 350 'F at an absolute pressure of mm. Hg for one The crude s'aponiiication number of 79. V l

l EXAMPLE n,

A mixture of 84gms. (0.45 mol) of tetraethylene pentarnine and 702 gins. (0.45 mol) of the polybutenyl succinic anhydride of Example II hereinabove, was blended with agitation at 125 F. in a nitrogen atmosphere.

The temperature was increased to 400 F. during a period of one hour, after which the absolute pressure was reduced to about 200 mm. Hg during a period of 30 minutes to facilitate the removal of water. The reaction mixture was then allowed to reach room temperature at this reduced pressure. The reaction product contained 5.1% nitrogen (theory=5.4%). Infra-red analysis showed that thereaction product was an imide containing a polybutene side chain.

, EXAMPLE III A mixture of 21.3 gms. (0.21 mole) of dimethylaminopropylamine and 150 gms. (6.09 mol) of the polybutenyl succinic anhydride of Examplell hereinabove, was blend ed with agitation in a nitrogen atmosphere, and the mixture was heated at 500 F. for a period of one hour, after which the absolute pressure was reduced to about pound may be suspended in a suitable liquid medium and 7 such as merely adding the. acid to the melted'polymeric 200 mm. Hg at this temperature during a period of minutes to facilitate the removal of water and excess amine. The reaction mixture was then allowed to reach room temperature at this reduced pressure. The reaction product contained 1.7% nitrogen (theory=1.8%). The identity of the N-dimethylaminopropylalkenyl succinimide was established by means of infra-red spectroscopy. Y

Other examples of cationic portions of additives used to form'sulfonate salts of the present invention include:

Olefinic-Suceinie Anhydride Amine Mole Temp,

' g Ratio F.

IV. Polyisobutylene (MW Diethylamine pro 1/1 420 850)-su ccinic anhydride. pylamine.

V. Polyisobutylene (MW 850) Tetraethylene- 1. 5/1 400 succinic anhydride; pentamine.

VI. 'Polyethylene/isobutyleue Dimethylamine V, 1/1 450 1,000succinic anhypropylamine.

VII. Polyethyleue/,methyl- Tetraethylene III 450 styrene (MW 800)succiuic peutamine.

anhydride. 7 a r VIII. Polyisobutylene (MW d0 p 1/1 400 1,000)succinic anhydride.

The anionic portion of 'the'salts of thepresent invention can be any organic sulfonic acid. Suitable organic sulfonic acids include benzene sulfonic acid, the alkyl benzene sulfonic acids, such as para-toluene sulfonic acid, p-octylbenzene sulfonic acid and .p-dodecylbenzene sulfonic acid, alphaand beta-naphthalene sulfonic acids, the alkylnaphthaline sulfonic acids, the naphthol sulfonic acids, alkyl sulfonic acids,. such as octyl sulfonic acid, and th'esulfonic acids made by the sulfonation of various 7 fractions derived from petroleum, such as the petroleum 'sulfonic acids made by the sulfonation of lubricating oil in a suitable solvent. Alternatively, the polymeric comcompound are also suitable on occasion.

It is notressential that'all the basic nitrogen-containing polymer be neutralized 'by the sulfonic acid and in such cases the final product'may be only from 19% to 50%, preferably from 26% to'40%.neutralized. This is particularly desirable if the salt is required to act as a detergent additive as well as a wear and corrosion inhibitor and viscosityindex improver.

The basic nitrogen-containing polymeric (aminoimide) salts of sulfonic acids used in oil compositions of the present invention are novel salts and form one feature of the present invention.

The following examples illustrate the preparation. of the novel salts provided by the present invention. these examples, the parts referred to are part by weight.

EXAMPLE 1A About 15 parts of the polymer of Ex. I was dissolved in 409 parts by volume of benzene, and 5.5 parts of petroleum naphtha-sulphonic acid were added. The mixture was refluxed under a Dean and Stark head until no more water separated. The benzene was distilled 05 under re duced pressure, the final traces, being removed on a steam bath at 0:1 mm. Hg pressure. The residue was the petroleum naphtha-sulphonate of the polymeric amino-inside compound of Ex. I.

EXAMPLE LIA The procedure of ExampleIA was followed, but using a mixture comprising 3.4 parts of the polymer of Ex. III which was dissolved in'lOOO parts by volume of benzene, and 10 parts of para-toluene sulphonic acid were added. The mixture was refluxed under a Dean and Stark head until no more water separated. The benzene was distilled otfunder reduced pressure, the final traces being removed on a steam bath or" 0.1 Hg pressure. The residue was the para-toluene sulphonate of the polymeric aminoimide of Ex. 1.: 7 EXAMPLE 111A EXAMPLE IVA 7 About 30 parts of the polymeric compound of Ex. IV

was dissolved in parts by volume of benzene and to this solution was added about 2.7 parts of petroleum sulfonic acid having. an acid valueof 104 mg. KOH/g.

(equivalent weight of about 560) which was dissolved in parts by volume of benzene. The sulfonate salt was prepared in Ex. IA. The resulting homogeneous solution- :as filtered'and the benzene distilled oil. The residue was the petroleum sulphonate of the polymeric aminoimide of IV. 7 EXAMPLE VA 5 parts of a hydrocarbon sulphonic acid, prepared by the sulphonation of an Edeleanu extract from kerosene and having an acid value of 330 mg. KOH/g. (equivalent weight of about ),.was refluxed with 20 parts of Ex. I additive in a benzene solution under conditions of Ex. IA

and the solution was filtered and the benzene distilled ofi, traces being removed under high vacuum at 100 C. to recover the residue which was the hydrocarbon sulphonate of the polymeric amino-imide of Ex. 1.

Other examples of additives of the invention include:

VIA. Oil-soluble salt of polymer of Ex. V and petroleum sulfonic acid.

VHA. Oil-soluble salt of polymer of Ex. HI and dodecyl benzene sulfonic acid.

VlTlA. Oil-soluble salt of polymer of Ex. V111 and petroleum sultonic acid.

lXA. Oil-soluble salt of Ex. TV and para-toluene sulfonic acid. 7

When desired, additional improvements with respect to oxidation stability and sending inhibition can be imparted to the oil compositions containing the polymer salts of this invention by incorporating small amounts (0.01%- 2%, preferably 0.1%1%) of phenolic antiox dants such as alkylphenols, e.g., 2,6-ditertbutyll-methylphenol or p,p'-methylene bisphenols such as 4,4'-methylene bis(2,6- ditertbutyl phenol) or arylamines such as phenyl-alphanaphthylamine; diallryl sulfides and mixtures thereof, e.g., dibenzyl disulfide, didodecyl sulfide. Anti-sending agents include organic phosphites, phosphates, phosphonates and their this-derivatives, such as C allryl phosphites, or phosphites, or phosphonates, e.g., diand tributyl, octyl, lauryl, stearyl, cyclohexyl, benzyl, cresyl, phenyl phosphites or phosphates, as well as their thio-derivatives, P S -terpene reaction products, e.g., P S -pine oil reaction product and alkali metal salts thereof such as a potassium salt of a P S -terpene reaction product, phosphonates such as dibutyl methanephosphonate, dibutyl trichloromethane phosphonate, dibutyl monochloromethanephosphonate, dibutyl chlorobenzenephosphonate,and the like. The full esters of pentavalent phosphorus acids such as triphenyl, tricresyl, trilauryl and tristearyl ortho-phosphates or potassium salt of P S -terpene reaction product are preferred.

The polymeric sulfonate salts when added to lubricating oils produce an outstanding lubricant. The lubricating oil can be any natural or synthetic oil having lubricating properties. Thus, the oil may be a hydrocarbon lubricating oil obtained from a parafiinic or naphthenic crude or mixtures thereof. The viscosity of these oils may vary over a wide range, such as from 60 SUS at 100 F. to 50 SUS at 210 F. The hydrocarbon lubricating oils may be blended with fatty oils, such as castor oil or lard oil, and/or with synthetic lubricating oils, such as polymerized olefins, copolymers or alkylene glycols and alkylene glycols and alkylene oxides, organic esters, such as di(eethyl hexyl) sebacate, dioctyl phthalate and trioctyl phosphate, polymeric teuahydroturane, and polyalkyl silicone polymore, such as dimethyl silicone polymers. The synthetic lubricating oils, such as polymeric hydrocarbons or the polar containing compounds may be used as the sole base lubricating oil or adrnixed with fatty oils and derivatives thereof. In formulating multigrade lubricants light oils of a viscosity range of 60 to 150 SUS at 100 1 are preferred of which light mineral oils of 75 to 100 SUS at 100 F. are specifically useful. For single grade lubricants high viscosity oils are prepared.

Lubricating compositions of the invention are illustrated by the following formulations:

Composition A The salt of Example 11A 1.5% by weight.

Mineral lubricating oil (75/100" F.

SUS) Essentially balance.

Composition B Composition C Mineral lubricating oil F.

SUS) Essentially balance.

Composition F The salt of Example HA 3% by weight. Zn dicyclohexyl thiophosphate 0.8% by weight. Mineral lubricating oil (100/ 100 F.

SUS) Essentially balance.

Composition G The salt of Example LA 4% by weight.

5% by weight.

4% by Weight.

Dicresyl phosphate 0.5% by weight. Mineral lubricating oil (100/ 100 F.

SUS) Essentially balance.

Compositions of the present invention were tested in the (1) Exhaust Gas Rust Test (EGRT) which comprises exposing oil-dipped steel panels to the exhaust vapors of a single cylinder 4-cycle Briggs and Stratton engine operating on a high sulfur (1%) fuel. The panels are exposed to the hot exhaust gases for 30 minutes, then cooled to a temperature of 0 F. for 16 hours and allowed to warm to room temperature. The cycle is then repeated before inspection and rated on a scale of 1 to 10, where 1 is poor and 10 is excellent; (11) and in the L38 engine test described in the SAE handbook 1962, page 275, and the results as shown in Table I.

TABLE I Test I II Composition E GRT 13-38 Test,

Rating Cu-Pb (1=poor, Strip loss 10=excel- (mg) lent) Composition A 8 5. 6 Composition 8 5. 0 Composition 0 9 0.7 Mineral lubricating oil 1 1% and dilanryl acid phosphates 4 50 Mineral lubricating oil 4% l-hydroxy ethyl- Z-heptadeeenyl irm'dazoline 2 48 Mineral lubricating oil 2% nonyl phcnoxy acetic acid 2 50 Mineral lubricating oil 2% l-hydroxy-etbyl- 2-heptadecenyl imidazoline 2% nonyl phenoxy acetic acid 2 50 Mineral lubricating oil 2% Ex. I additlve 1 50 Mineral lubricating oil 2% 1-hydroxy-ethyl- Z-heptadecenyl irnidazoline salt of petroleum sulfonic a 2 48. 6 Mineral lubricating oil 1 50 1 Viscosity of base oil 75 SUS at 100 F.

Lubricating compositions of the present invention can be used in automotive, truck, aeroplane, caterpillar and diesel engines a well as various industrial equipment.

We claim as our invention:

1. A lubricating composition comprising a major amount of lubricating oil and minor amount, sufficient to impart detergency and prevent wear, of a nitrogencontaining non-ash forming detergent salt of an aminoimide of a mono C polymeric hydrocarbyl substituted succinic anhydride the amine used to form the amino-imide being an aliphatic polyamine having at least 2 amine groups and an organic sulfonic acid the acid being present in an amount sufficient to neutralize at least 10% of the amino-imide compound.

2'. A lubricating composition comprising a major amount of lubricating oil and minor amount, sufiicient to impart detergency and prevent wear, of a nitrogen-containing non-ash forming detergent salt ofan' amino-imide of a mono 020400 polymerichydrocarbyl substituted succinic anhydride the amine used to form the -amino-imide being an aliphatic polyamine having at least 2 amine groups and an aromatic sulfonic acid the 'acid being present inan amount sufiicient to neutralizeat least 10% of the amino-imide compound.

r 3. A lubricating composition comprising a major amount of lubricating oil and'minor amount, sufficient to impart detergency and prevent Wear, of an oil-soluble detergent salt of an amino-imideiofa mono (32 35 polyolefin substituted succinicanhydr'ide, the amine used to form V the amino-imide being apolyalkylene polyamine having at least 2 amine groups and an aromatic sulfonic acid the acid being present in an amount sufficient to neutralize at least 10% of the amino-imide compound.

4. A lubricating composition comprising a major amount 0t lubricating oil and minor amount, sufficient to impart detergency and prevent Wear, of an oil-soluble detergent salt of an amino-irnideof a mono C polyolefin substituted succinic anhydride, the amine used to form the amino-imide being'a polyalkylene polyamine having at least 2 amine groups, and an oil-soluble petroleum sulfonic acid the acid being present in an amount sufficient to neutralize at least 10% of the amino-imide compound.

5. A lubricating oil composition comprising a major amount of mineral lubricating oil and minor amount, suificient to impart detergency and prevent wear, of an oil soluble detergent salt of an aliphatic amino-imide of monopolyisobutylene substituted succinic anhydride the amine used to form the amino-imide being a polyethylene polyamine having up 1:05 amine groups, the, polyisobutylene radical having a molecular weight of from 500 to 3000 and an oil-soluble petroleum sulfonic acid, the acid being present in an amount sufiicient to neutralize at least 50% of the amino-imide compound.

6. A lubricating oil composition comprising 'a major amount of mineral lubricating oil and minor amount of each of (1)" an oil-soluble detergent salt of an aliphatic amino-imide of mono-polyisobutylene substituted succinic anhydride the amine used to form the amino-imide being a polyethylene polyamine having up to amine groups, the polyisobutylene radical having a molecular Weight of from-500 to 3000, and an oil-soluble petroleum sulfonic acid, the acid being present in an amount sufficient to neutralize at least 50% of the amino-inside compound and (II) bis(di-C alkyl hydroXyl-phenyDmethane.

7. A lubricating oil composition comprising a major amount of mineral lubricating oil and minor amounts, sutficient to impart detergency and. prevent Wear and deterioration of the oil of each of (I) an oil-soluble detergent salt of an aliphatic amino-imide of monopolyisobutylene substituted succinic anhydride the amine used to form the amino-imide being'a polyethylene polyamine having up to 5 amine groups, the polyisobutylene radical having a molecular weight of from 500 to 3000, an oilsoluble petroleum sulfonic acid, the acid being present in teases an'amount sumcient to neutralize at least 50% of the amino-imide compound and (i1) diteitbutyl phenol). V

3. A lubricating oil composition comprisinga major 4,4'-methylene bis(2,6-

5 amount of mineral lubricating oil and minor amounts, suliicient to impart detergency and prevent'wear and dephate. V v

9. Oil-soluble detergent salt of an amino-imide of a mono 5 polymeric'hydrocarbyl substituted succinic anhydride the amine used to form the amino-imide being an aliphatic polyamine having at least'2 amine groups and an organic sulr'onic acid the acid being present in an amount sufficient toneutralize at least 10% of the aminoimidercompound; l0. Oil-soluble detergent salt'of an amino-imide of a mono C polymeric hydrocarbyl substituted succinic anhydride the amine used to form the amino-imide being an aliphatic polyamine having at least 2 amine groups and an aromatic sulfonic acid the acid being present in an'amount sufficient to neutralize' at least 10% of-the amino-imide compound.

'11. Oil-soluble detergent salt of an amino-imide of a mono C polyolefin substituted succinic anhydride, the amine used to form the amino-imide being a polyalkylene polyamine having at least 2 amine groups, and an aromatic sulfonic acid the acid being present in an amount sufiicient to neutralize at least 10% of the am'no-imide compound.

'12. Oil-soluble detergent salt of an amino-imide of a mono C polyolefin substituted succinic anhydride, the amine used to form the amino-imide being a polyalkylene polyamine having at least 2 amine groups,'and' References Qited by the Examiner" UNITED STATES PATENTS 7 2,862,883 12/58 Hughes et al. 25233 3,018,247 1/62 Anderson et a1. 25 2'51{5 3,025,240 3/62 Sheldahl 25233 3,038,857 6/62 Thomas 252-33 3,041,279 6/62 Calhoun et al. 25232.7 3,037,936 4/63 Le Suer .l 25 251.5;'

nANinL a. WYMAN, Primary Examiner.

amino-imide compound and (11) 4,4f methylene bis(2,6- ditertbutyl phenol) and (III) zinc dicyclohexylthiophos- Notice of Adverse Decision in Interference In Interference No. 95,732 involving Patent No. 3,189,544, H. Ratner and R. F. Bergstrom, NON-ASH-CONTAINING LUBRICATING OIL COM- POSITION, final judgment adverse to the patentees was rendered J an. 30, 1969, as to claims 1, 3, 10 and 11.

[Ofiicial Gazette August 5, 1969.]

Claims (1)

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR AMOUNT OF LUBRICATING OIL AND MINOR AMOUNT, SUFFICIENT TO IMPART DETERGENCY AND PREVENT WEAR, OF A NITROGENCONTAINING NON-ASH FORMING DETERGENT SALT OF AN AMINOIMIDE OF A MONO C20-300 POLYMERIC HYDROCARBYL SUBSTITUTED SUCCINIC ANHYDRIDE THE AMINE USED TO FORM THE AMINO-IMIDE BEING AN ALIPHATIC POLYAMINE HAVING AT LEAST 2 AMINE GROUPS AND AN ORGANIC SULFONIC ACID THE ACID BEING PRESENT IN AN AMOUNT SUFFICIENT TO NEUTRALIZE AT LEAST 10% OF THE AMINO-IMIDE COMPOUND.