US3844958A

US3844958A - Hydrocarbyl amines for lubricating oil detergents

Info

Publication number: US3844958A
Application number: US00647632A
Authority: US
Inventors: R Anderson; L Honnen
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1965-08-23
Filing date: 1967-06-21
Publication date: 1974-10-29
Anticipated expiration: 1991-10-29

Abstract

Hydrocarbon substituted amines and alkylene polyamines, substantially free of aromatic unsaturation, having molecular weights in the range of about 450 to 10,000 find use as detergents in lubricating oils.

Description

Z Sttes atom Anderson et al..

[4 1 Oct. 29, 1974 HYDROCARBYL AMINES FOR LUBRHCATING OIL DETERGENTS Inventors: Robert G. Anderson; Lewis R.

Honnen, both of Novato, Calif.

Assignee: Chevron Research Company, San

Francisco, Calif.

Filed: June 21, 1967 App]. No: 647,632

Related U.S. Application Data Continuation-in-part of Ser. Nos. 488,775, Sept. 20, 1965, Pat. No. 3,574,576, and Ser. No. 481,916, Aug. 23, 1965, abandoned, and Ser. No. 408,686, Nov. 3, 1964, abandoned.

US. Cl. 252/32] E, 252/50, 252/5l.5 R, 260/247, 260/268, 260/293, 260/315, 260/568, 260/577, 260/578, 260/583, 260/584 Int. Cl..... Cl0m 1/48, C10m 1/20, Cl0m 1/32 Field of Search 252/50, 51.5, 32.7 E; 260/247, 268, 293, 583, 584, 568, 577, 578, 307, 315

Noller, Chemistry of Organic Compounds, Pub. by W. B. Saunders Co., Phila, Pa.( 1951), pages 225 & 694.

Primary ExdmineF-Patrick P. Garvin Attorney, Agent, or Firm-G. F. Magdeburger; C. J. Tonkin [57] ABSTRACT Hydrocarbon substituted amines and alkylene polyamines, substantially free of aromatic unsaturation, having molecular weights in the range of about 450 to 10,000 find use as detergents in lubricating oils.

13 Claims, No Drawings I-IYDROCARBYL AMINES F OR LUBRICATING OIL DETERGENTS CROSS-REFERENC ES TO RELATED APPLICATIONS This application is a continuation-in-part of applications Ser. Nos. 488,775, filed Sept. 20, 1965, now U.S. Pat. No. 3,574,576; 481,916, filed Aug. 23, 1965, now

abandoned; and 408,686, filed Nov. 3, 1964, now

abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention In order to prevent deposits on engine parts, detergent and dispersant additives are included in modern day lubricating oils. The dispersants and detergents maintain sludge which is formed in the oil dispersed in the oil and aid in removing deposits from motor surfaces and dispersing the deposits. Not only must the dispersant-detergent prevent formation of deposits, but the additive must itself not contribute to deposits. Recently, in about the last ten years, new dispersant and detergent additives have been provided for lubricating oils for internal combustion engines which are not inorganic salts of organic acids, but rather are polar amine derivatives.

2. Description of the Prior Art Numerous patents have issued concerned with carboxyl derivatives of alkylene polyamines, as well as other amines. See U.S. Pat. Nos. 3,219,666, 3,018,250, 3,172,892 and 3,272,746.

SUMMARY OF THE INVENTION Relatively high molecular weight aliphatic branched chain hydrocarbon substituted amines are provided having molecular weights in the range of about 450 to 10,000 and having at least one branched chain hydrocarbon radical of at least 400 molecular weight. These compositions are useful as detergents in lubricating oils used under a wide variety of operating conditions.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The compositions of this invention will for the mo part have the following formula:

The above symbols are defined as follows:

A hydrogen, hydrocarbyl of from one to 10 carbon atoms, and hydroxyhydrocarbyl of from one to 10 5 carbon atoms Z hydrogen, hydrocarbyl or hydroxyhydrocarbyl of from one to 10 carbon atoms and may be taken together with A to form a ring of from 5 to 6 annular members and up to 12 carbon atoms U alkylene of from two to six carbon atoms, there 6 a 2b an integer of from 1 to 10 c an integer of from 1 to 5 and over the entire composition is on the average a number in the range of l to 4, and is equal to or less than the number of nitrogen atoms in the molecule x an integer of from 0 to l y an integer of from 0 to l x+yequaltol The hydrocarbon radical indicated by R may have a variety of structures, aliphatic or alicyclic, generally free of aromatic unsaturation and relatively free of aliphatic unsaturation That is, there will usually not be more than about 2 sites of olefinic unsaturation and generally not more than 1 site of olefinic unsaturation.

Usually, the hydrocarbon radical will be prepared by polymerizing olefins of from two to six carbon atoms (ethylene being copolymerized with another olefin so as to provide a branched chain). Alternatively, the hydrocarbon radical may be derived from naturally occurring products of high molecular weight, e.g., naphthenic bright stock.

The branched chain hydrocarbon radical will generally have at least 1 branch per six carbon atoms along the chain, preferably at least 1 branch per four carbon atoms along the chain and particularly preferred that there be at least 1 branch per two carbon atoms along the chain. That is, the preferred branched chain hydrocarbon radicals are polypropylene and polyisobutylene. The branches will be of from one to two carbon atoms, usually 1 carbon atom, i.e., methyl.

In most instances, the compositions of this invention are not a pure single product, but rather a mixture of compounds having an average molecular weight. Usually, the range of molecular weights will be relatively narrow and peaked near the indicated molecular weight. Similarly, for the more complicated polyamines, the compositions will be a mixture of amines having as the major product the compound indicated as the average composition and having minor amounts of analogous compounds relatively close in composition to the dominant compound.

Monoamines The compositions which will be considered first are those where y is O.

The monoamine compositions will have the following formula:

RNAZ

The above symbols are defined as follows:

R a branched chain hydrocarbon radical, substantially free of unsaturation, particularly aromatic unsaturation, usually of from about 425 to about 3,000 molecular weight, preferably up to 1,500 molecular weight, and particularly preferred of polypropylene or polyisobutylene A hydrogen, hydrocarbyl or hydroxyhydrocarbyl of from 1 to 10 carbon atoms, preferably aliphatic, and usually hydrogen, alkyl or hydroxyalkyl of from 1 to 6 carbon atoms, more usually of from 1 to 3 carbon atoms Z the same or different from A and hydrogen, hydrocarbyl or hydroxyhydrocarbyl of from one to 10 carbon atoms, preferably aliphatic, and usually hydrogen, alkyl or hydroxyalkyl of from one to six carbon atoms, more usually of from one to six carbon atoms Z and B when taken together with the nitrogens to which they are attached form a ring having 5 to 6 annular members, which may have from to 1 oxygen atom as an annular member to form, for example, morpholine illustrative compositions include polypropenyl amine, polyisobutenyl amine, N-polyisobutenyl dimethylamine, N-polyisobutenyl methylethylamine, N- polypropenyl diethylamine, N-polypropenyl di(2- hydroxyetnyl) amine, N-polyisobutenyl N-methyl aniline, N-polyisobutenyl morpholine, N-polyisobutenyl piperidine, N-poly( l-butene) propylamine, N polypropenyl N-(Z-hydroxyethyl) amine, etc.

Preferred monoamine detergents and dispersants for lubricating oils have the following formula:

R"NHA The above symbols are defined as follows:

R a branched chain aliphatic hydrocarbon radical of from about 50 to 200 carbon atoms A hydrogen or lower alkyl The preferred hydrocarbon radicals are polyisobutylene and polypropylene. Polyamines Turning now to a consideration of the compositions when .r is 0, these compositions, for the most part, will be described by the following formula:

The above symbols are defined as follows:

U alkylene of from two to six carbon atoms, there being at least two carbon atoms between the nitrogen atoms and preferably of from two to three carbon atoms R" a hydrocarbon radical substantially free of aromatic unsaturation (less than 5 number of the carbon atoms are incorporated in aromatic systems) and usually a branched chain aliphatic hydrocarbon radical of from about 400 to 5,000 molecular weight, preferably of from 400 to 3,000 molecular weight a an integer of from 0 to 10, preferably 0 to 6 b an integer of from 0 to l a 2b an integer of from 1 to 10, preferably 1 an integer of from I to 4, and on the average over the entire composition a number in the range of about 1 to 3, there being fewer R groups than nitrogen atoms averaging over the entire composition The alkylene radical indicated as U will have from two to six carbon atoms and more usually, from two to three carbon atoms, the nitrogen atoms connected by U being separated by at least two carbon atoms. The alkylene group may be straight chain or branched and is preferably polymethylene of from two to three carbon atoms.

Illustrative alkylene groups are ethylene, 1,2- propylene, 2,2-dimethyl propylene-1,3, trimethylene, hexamethylene, 2-methyll ,3-propylene, etc.

The alkylene polyamines which are substituted with the hydrocarbon radical may be derived from such alkylene amines as ethylene diamine, diethylene triamine, tetraethylene pentamine, nonaethylene decamine,

-4 2-aminoethyl piperazine, 1,3-propylene diamine, 1,2- propylene diamine, tetramethylene diamine. etc.

As already indicated, in many instances a single compound will not be used as a reactant in the preparation of the compositions of this invention. That is, mixtures will be used in which l or 2 compounds will predominate and the average composition or molecular weight is indicated. For example, tetraethylene pentamine prepared by the polymerization of aziridine or reaction of dichloroethylene and ammonia will have both lower and higher members, e.g., triethylene tetramine and pentaethylene hexamine, but the composition will be mainly tetraethylene pentamine and the empirical formula of the total composition will closely approximate that of tetraethylene pentamine. Similarly, the molecu' lar weight reported for the branched chain aliphatic hydrocarbon group is an average for a mixture which is sharply peaked-when graphing the number average molecular weight distribution. Also, when the nitrogens of the alkylene polyamines are not equivalent, substitution on different nitrogens will afford different compounds.

As is evident from the above formulae, the alkylene polyamines may have only 1 hydrocarbon substituent or may be polysubstituted with hydrocarbon radicals. The mono-substituted alkylene polyamine compositions will have the following formula:

The above symbols are defined as follows:

(1 an integer of from 0 to 5, preferably of from 0 to 4 b an integer of from 0 to 1, preferably 0 when at is greater than 0 a 2b an integer of from 1 to 5 d an integer of from 2 to 3 R a branched chain aliphatic hydrocarbon radical derived from polymerizing olefms of from three to six carbon atoms, preferably of from three to four carbon atoms, and particularly preferred of propylene and isobutylene and having a molecular weight in the range of 400 to 3,000, preferably 400 to 2,500 Illustrative compounds within the above formula are as follows: N-polyisobutenyl ethylene diamine, N- polypropenyl ethylene diamine, N-poly( l-butenyl) ethylene diamine, N-(alternating copolymer of ethylene and isobutylene) ethylene diamine (alternating copolymers of ethylene and isobutylene may be achieved by the cationic polymerization of 4-methylpentene-l N- polypropenyl Z-aminoethylpiperazine, N- polyisobutenyl Z-aminoethylpiperazine, N- polypropenyl diethylene triamine, N-polyisobutenyl diethylene triamine, N-poly(l-pentenyl) diethylene triamine, N-polypropenyl trimethylene diamine, N- polyisobutenyl trimethylene diamine, N-polypropenyl di(trimethylene) triamine, N-polyisobutenyl di(- trimethylene) triamine, N-polyisobutenyl l ,2- propylene diamine, N-polyisobutenyl di( 1 ,2-

propylene) triamine, N-polypropenyl triethylene tetramine, N-polyisobutenyl triethylene tetramine, N- (alternating copolymer of ethylene and isobutylene) triethylene tetramine, N-polypropenyl tetraethylene pentamine, N-polyisobutenyl tetraethylene pentamine, N-polyisobutenyl pentaethylene hexamine, etc.

The poly(hydrocarbon radical)substituted alkylene polyamine compositions have the following formula:

The above symbols are defined as follows:

a an integer of from to 5, preferably an integer of from 1 to 4 b an integer of from 0 to 1, preferably 0 when a is greater than 0 a 2b an integer of from 1 to 5 c an integer in the range of l to 3, averaging over the composition fewer R groups than nitrogen atoms d an integer of from 2 to 3 R a branched chain aliphatic hydrocarbon radical either free of or having aliphatic unsaturation, e.g., olefinic and of from 400 to 3,000 molecular weight, preferably of from 400 to about 2,500 molecular weight (As indicated by the above formula, the number of hydrocarbon substituents need not be a whole number when averaged over the total composition; generally, a mixture will be obtained containing mono-, diand trior higher substituted molecules averaging out to a fractional or whole number.)

Illustrative compounds coming within the above formula are as follows: N,N-di(polypropenyl) diethylene triamine, N,N-di(polyisobutenyl) diethylene triamine, N,N-di(polyisobutenyl) triethylene tetramine, N,N- di(polypropenyl) tetraethylene pentamine, N,N- di(polyisobutenyl) tetraethylene pentamine, N,N,N- tri(polyisobutenyl) tetraethylene pentamine, N,N- di(polyisobutenyl) Z-aminoethylpiperazine, N,N-di(poly-l-butenyl) triethylene tetramine, N,N- di(polyisobutenyl) di-(trimethylene) triamine, etc.

The preferred compositions are those having the straight chain alkylene polyamines, particularly ethylene diamine and polyethylene polyamines. These compositions have the following formula:

The above symbols are defined as follows:

a an integer of from 1 to 5, preferably of from 1 to 4 c an integer of from I to 3, preferably of from l to 2, per molecule there being fewer R groups than nitrogen atoms R a branched chain aliphatic hydrocarbon radical of from 400 to 3,000 molecular weight, preferably of from 400 to 2,500 molecular weight, and, particularly preferred, either polypropenyl or polyisobutenyl Synthesis The compositions of this invention are readily prepared by combining an aliphatic or alicyclic halide with the desired amine in the proper mole proportions. The halide is prepared from the hydrocarbon by halogenation: ionically or free radically.

As already indicated, the hydrocarbon groups may be prepared by ionic or free radical polymerization of olefins of from 2 to 6 carbon atoms (ethylene must be copolymerized with another olefin) to an olefin of the desired molecular weight. The olefins which find use are ethylene, propylene, isobutylene, l-butene, l-pentene, 3-methyl- 1 -pentene, 4-methyll -pentene, etc., preferably propylene and isobutylene.

As previously indicated, there should be at least I branch per six carbon atoms along the chain and preferably at least 1 branch per four carbon atoms along the chain. The preferred olefins, propylene and isobutylene, have from 0.5 to l'branch per atom along the hydrocarbon chain.

Alternatively, various naturally occurring materials may be used which have the desired molecular weight and aliphatic or alicyclic character.

The halogen may be introduced into the hydrocarbon molecule by various means known in the art. Most readily, either chlorine or bromine (halogen of atomic number 17-35) may be introduced by the free radical catalyzed halogenation of the hydrocarbon, or ionic addition to olefinic unsaturation. Various free radical catalysts may be used, such as peroxides, azo compounds, bromine, iodine, as well as light. Ionic catalysts are exemplified by ferric chloride. Methods of halogenation are well known in the art and do not require extensive exemplification or illustration here.

The amount of halogen introduced will depend on the particular hydrocarbon used, the desired amount of amine to be introduced into the molecule, the particular alkylene amine used, and the halogen used. The amount of halogen introduced will generally be in the range from about 1 to 5 halogen atoms per molecule, depending on the reactivity of the resulting halide. On a weight per cent basis, the amount of halide will generally range from about 1 to 25, more usually from about 1 to 10.

The halohydrocarbon and amine may be brought together neat or in the presence of an inert solvent, particularly a hydrocarbon solvent. The inert hydrocarbon solvent may be aliphatic or aromatic. Also, aliphatic alcohols may be used by themselves or in combination with another solvent, when capable of dissolving the reactants.

The reaction may be carried out at room temperature (20C.), but elevated temperatures are preferred. Usually, the temperature will be in the range of from about to 225C. Depending on the temperature of the reaction, the particular halogen used, the mole ratios and the particular amine, as well as the reactant concentrations, the time may vary from 1 to 24 hours, more usually from about 3 to 20 hours. Times greatly in excess of 24 hours do not particularly enhance the yield and may lead to undesirable degradation. It is therefore preferred to limit the reaction time to fewer than 24 hours.

The mole ratio of halohydrocarbon to amine will generally be in the range from about 0.2 to 20 moles of amine per mole of halohydrocarbon, more usually 0.5 to 10 moles of amine per mole of halohydrocarbon.

The mole ratio willdepend upon the amount of halogen present in the halohydrocarbon, the particular halogen and the desired ratio of hydrocarbon to amine. lf com plete suppression of polysubstitution of the alkylene polyamines is desired, then large mole excesses of the amine will be used.

Small amounts of residual halogen in the final composition are not deleterious. Generally, the residual halogen as bound halogen will be in the range of 0 to 10 weight per cent of the composition. Small amounts of halogen may be present as the hydrohalide salt of the hydrocarbon substituted alkylene polyamines.

Generally, the hydrocarbons used will have aliphatic unsaturation. In particular instances, the amines may react in a way resulting in the elimination of hydrogen halide, introducing further aliphatic unsaturation into the hydrocarbon radical. Therefore, the hydrocarbon radicals usually will be olefinically unsaturated. How-- ever, the olefinic unsaturation does not significantly affeet the utility of the product, and when available, saturated aliphatic halide may be used.

After the reaction has been carried out for a sufficient length of time, the reaction mixture may be extracted with a hydrocarbon medium to free the product from any low molecular weight amine salt which has formed. The product may then be isolated by evapora-. tion of the solvent. Further separation from unreacted hydrocarbon or purification may be carried out as desired, e.g., chromatography. 1

Depending on the particular application of the com position of this invention, the reaction may be carried out in the medium in which it will ultimately find use and be formed at concentrations which provide a concentrate of the detergent composition. Thus, the final reaction mixture may be in a form to be used directly upon dilution in lubricating oils.

As has already been indicated, the compositions encompassed by this invention have a broad spectrum of. uses as detergents and dispersants. Not only do they find use as detergents and dispersants in lubricating oils under the hot" conditions of the diesel engine and the relatively cooler conditions of the automobile internal combustion engine, where wide fluctuations in temperature occur, but the detergents of this invention may also be used in Z-cycle spark ignition engines-where the lubricating oil containing the detergent is introduced into the fuel.

Because of the broad changes in conditions under which the compositions of this invention will operate, there will be to some degree, preferred subgenera for the various uses. Moreover, depending on the particular use, different additives will be used in conjunction with the detergents and the dispersants of this invention. Finally, obviously the media in which the detergents and the dispersants will be employed will vary depending on how the lubricating oil is to be employed.

Preferred polyamine detergents and dispersants for lubricating oils for automobile and diesel engines have the following formula:

The detergents may be prepared as concentrates having as high as weight per cent of the detergent in Inbricating oil. Generally, concentrates will vary from about 10 to 80 weight per cent. However, when the oil is to be used in the engine, the amount of the detergent generally will vary from about 0.1 to l5 weight per cent, more usually from 0.25 to 10 weight per cent. The lubricating oil compositions may therefore vary in the amount of detergent from 0.] to 80 weight per cent.

The compositions of this invention can be used with various base oils which find use as lubricating oils. Naturally occurring base oils include naphthenic base, paraffin base, asphaltic base and mixed base lubricating oils. Synthetic hydrocarbon oils include alkylene poly-. mers, such as polymers of propylene, butylene, l-- octene, and mixtures thereof and alkylated aromatic hydrocarbons. Nonhydrocarbon lubricating oils in- .clude: alkylene oxide type polymers; carboxylic acid esters such as octyl adipate, nonyl a'zelate, decyl suberate, butyl alkenylsuccinate, etc.; also, inorganic esters such as phosphates and silicates.

The above base oils may be used individually or in combination, whenever miscible or made so by the use of mutual solvents.

Preferably, the detergents of this invention are used in lubricating oils with an oxidation inhibitor and extreme pressure agent. The preferred inhibitors are metal dithiophosphates, particularly zinc 0,0-di(hydrocarbyl) phosphorodithioate, where the hydrocarbyl groups are generally from 4 to 36 carbon atoms. (Hydrocarbyl is an organic radical composed solely of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl or alkaryl, and may be aliphatically saturated or unsaturated, e.g., ethylenic unsaturation.) Preferably, the hydrocarbyl groups are alkyl or alkaryl groups. Also, S-alkyl and S- polyalkyleneoxy esters of the phosphorodithioate may be used. Usually, about 6 to 50 mM./kg. of the phosphorodithioate is used in the oil.

Other additives may also be included in the lubricating oil. These additives include pour point depressants, viscosity index improvers, antiwear agents, rust inhibitors, corrosion inhibitors, other detergents and dispersants, etc. Generally, the total amount of additives exclusive of the detergent will be in the range of from about 0.1 to 5 weight per cent of the luricating oil composition.

A special situation in which the lubricating oil is employed is the 2-cycle spark ignition engine. With the 2- cycle engine, the oil is incorporated with the fuel and burned directly in the piston chamber. The oil/gasoline mixture first enters the crankcase where the mixture of lubricant and unvaporized fuel contacts and lubricates the various moving parts including the bearings, pistons, piston rings and cylinders. Any lubricant that does not deposit on the surfaces in the lower part of the engine passes into the combustion chamber where it is burned along with the fuel. An effective detergent solubilizes any deposit precursors and the deposit precursors are carried into the combustion chamber and burned. While the dispersant and detergent are considered a lubricating oil additive, the detergent operates in a mixed lubricating oil-fuel environment.

Preferred polyamine compositions for use in the 2- cycle engine have the following formula:

The above symbols are defined as follows:

a an integer of from 1 to 4 c an integer of from 1 to 2, preferably about 1 R a branched chain aliphatic hydrocarbon radical having a molecular weight of from about 750 to 1,500, preferably a polymer of propylene or isobutylene Illustrative compounds which come within the above formula are polyisobutenyl ethylene diamine, polypropenyl ethylene diamine, as well as the previously indicated compounds which are included in the above formula.

For 2-cycle engine oils, hydrocarbonaceous lubricating oils will be used, particularly petroleum derived, such as the mixed base, paraffinic and naphthenic base oils. Moreover, in place of phosphorodithioate inhibitors, other oxidative inhibitors such as bis(phenols), etc. may be used. When phosphorodithioate additives are used. concentrations in the oil may be as low as l mM./kg. Finally, a halide scavenger for the lead will also be added, usually to enhance the halide already present in the gasoline. Alkylene halide scavengers such as ethylene dibromide may be used with the detergent compositions of this invention, but aryl halides, e.g., dichlorobenzene, are preferred. Other additives, already described for the lubricating oils, may also be included.

The following examples are offered by way of illustration and not by way of limitation.

Preparations of Halogenated Hydrocarbons Example A lnto a reaction flask was introduced 950 g. of polyisobutylene (approximate average molecular weight The mixture was stirred and chlorine was introduced at a rate of 235-250 ml. per minute, the temperature being maintained at 0C. After the reaction mixture had taken up 51 g. ofchlorine, the introduction of chlorine was terminated, the carbon tetrachloride removed in vacuo and the chlorinated polyisobutylene isolated and analyzed. Analysis: wt. 7t chlorine, 7.0.

Example B lnto a reaction flask was introduced 225 g. of N- bromosuecinimide, 750 g. of polyisobutylene (approximately 930 average molecular weight) and 750 ml. of carbon tetrachloride, the flask swept with nitrogen and the solution heated to 70C. while maintaining a positive nitrogen pressure on the flask. To the solution was then added dropwise 0.5 g. of benzoyl peroxide in 50 ml. of carbon tetrachloride. At the end ofthe addition, the solution was cooled and the succinimide filtered off. The carbon tetrachloride was removed in vacuo. Analysis: wt. "/1 bromine, 8.86, 8.80.

Example C I lnto a reaction flask was charged 5,000 g. of polyisobutylene weight) and 2 kg. of benzene. With stirring, chlorine gas was introduced at a rate of about 235 ml. per minute and the reaction allowed to proceed for about hours. Any dissolved hydrogen chloride was removed by heating the solution at reflux for about 1 to 2 hours. Analysis: wt. /r: chlorine, 4.21.

Example D lnto a reaction flask was charged 910 g. of polyisobutylene (approximately 950 average molecular weight) and 625 ml. of carbon tetrachloride and the solution (approximately 950 average molecular purged with nitrogen. Chlorine was introduced at a 5 flow rate (Fisher and Porter No. 9144 flow meter) for 2 hours and 35 minutes while maintaining the temperature at about 8 to 10C. The reaction mixture was then purged with nitrogen and the carbon tetrachloride stripped in vacuo, the pot temperature reaching 120C. and the final pressure being 5 mm. Hg. Analysis: wt. chlorine, 4.48. Preparation of Substituted Amines Example I lnto a reaction flask was introduced 873 g. of bromopolyisobutylene (polyisobutylene of approximately 930 average molecular weight brominated to 4.93 weight per cent bromine) and 87 g. of tetraethylene pentamine (a mixture of compounds having the average composition of tetraethylene pentamine). The reaction was stirred for one-half hour and then heated to 185C. for about 18 hours. At the end of this time, the mixture was allowed to cool, diluted with 3 volumes of n-hexane, and the hydrobromide salt permitted to settle. The supernatant liquid was then decanted and the remaining salt extracted with ethanol and water. After evaporation of the volatile material, the final product analyzed as follows: wt. nitrogen, 1.1; wt. bromine, 0.2.

Example 2 Into a reaction flask was introduced 800 g. of a chlorinated paraffimic base oil (averagemolecular weight approximately 570 chlorinated to approximately 6.4 weight per cent) and g. of tetraethylene pentamine and the mixture heated at 185C. for 6 hours. At the end of this time, the reaction mixture was cooled and diluted with 3 volumes of n-hexane and 1 volume of ethanol followed by dilute sodium carbonate and water washes. The mixture was then heated to reflux and then dilute sodium carbonate was added until the cloud pointwas reached, the phases separated, the organic phase diluted with one volume of ethanol, and then the mixture extracted with water. The volatile products were then pumped from the organic phase. Analysis: wt. nitrogen, 0.53; wt. basic nitrogen, 0.36.

Example 3 lnto a reaction flask was introduced 1,780 g. of brominated polyisobutylene (polyisobutylene of approximately 930 average molecular weight brominated to 8.6 weight per cent bromine) and 350 g. of a mixture of polyethylene amines having an average composition of tetraethylene pentamine and allowed to stand overnight at ambient temperatures. The mixture was then heated at 150C. for several hours (approximately 5 to 6), cooled and diluted with several volumes of npentane and allowed to stand. The solution was then concentrated to about one-half its original volume, about 1 liter of ethanol and about 1 liter of 10 per cent aqueous sodium carbonate added. The phases were separated and the sodium carbonate extraction re peated, followed by washing the hexane phase with water. Volatile materials were removed in vacuo by heating the organic phase to C, leaving a residue of 1,369 g. Analysis: wt. nitrogen, 2.26, 2.21; wt. basic nitrogen, 1.09; wt. bromine, 1.08, 0.99; molecular wt., 2,318 (determined by ThermoNAM, a differential vapor pressure technique).

Example 4 lnto a reaction flask was introduced 433 g. of chlorinated polyisobutylene (polyisobutylene of approximately 950 average molecular weight chlorinated to 9.3 weight per cent. chlorine) and 240 g. of alkylene polyamine having an average composition of tetraethylene pentamine and 640 ml. of benzene added. The mixturewas'heated to reflux and the benzene distilled off. The residue was then heated at 150C. for 4 hours. After cooling the reaction mixture and diluting with mixed hexanes, 200 ml. of ethanol was added and the organic phase extracted with 10 weight per cent aqueous sodium carbonate, the phases separated and the extraction of the organic phase repeated, the phases separated again and finally the organic phase washed with water. The volatile materials were then removed in vacuo. Analysis: wt. nitrogen, 4.66, 4.76; wt. chlorine, 3.16; molecular wt. (ThermoNAM), 1,318.

Example 5 lnto a pressure vessel was introduced 1,500 ml. of a solution of 5 parts of chlorinated polyisobutylene (approximately l,300 molecular weight) and 2 parts of benzene (the solution analyzing to 3.66 weight per cent chlorine) and 300 g. of ethylene diamine (the vessel sealed and heated at 150C. with rocking overnight). The vessel was then allowed to cool, vented and to the reaction mixture was added an equal volume of nhexane and a one-third volume of ethanol, the resulting mixture being heated to reflux. Approximately onethird volume of water was then added, the phases separated and the hydrocarbon phase isolated. The volatile materials were removed in vacuo and the residue analyzed. Analysis: wt. nitrogen, 1.82, 1.83; wt. basic nitrogen, 1.65, 1.63.

Example 6 lnto a reaction flask was introduced 3,000 g. of a 70 weight per cent solution in benzene ofchloropolyisobutylene (polyisobutylene of approximately 1,300 molecular weight chlorinated to 4.3 weight per cent chlorine) and 210 g. of alkylene polyamine having an average composition of triethylene tetramine and the mixture heated to reflux, the benzene stripped off and the mixture further heated at 170C. for 4 hours. At the end of this time, the mixture was allowed to cool, and then diluted with equal volumes of mixed hexanes and absolute ethanol, heated to reflux and then one-third volume of weight per cent aqueous sodium carbonate added. The phases were separated, and the organic phase washed with water and then the volatile materials removed in vacuo. Analysis: wt. nitrogen, 1.44; wt. 7( basic nitrogen, 0.89; wt. 7( chlorine, 1.45; molecular weight (ThermoNAM), 2,419, 2,371.

Example 7 Following the procedure described in Example 6, 1,500 g. of a 70 weight per cent solution in benzene of chloropolyisobutylene (polyisobutylene of approximately 950 molecular weight chlorinated to -10 weight per cent) and 155 g. ofdiethylene triamine were combined. Analysis: wt. nitrogen, 1.59, 1.60; wt. basic nitrogen, 0.96, 0.97. I

Example 8 lnto a reaction flask was introduced 800 g. of benzene, 846 g. ofchlorinated polyisobutylene (polyisobutylene of approximately 950 molecular weight chlorinated to 5.6 weight per cent) and 300 g. of alkylene polyamine having an average composition of triethylene tetramine and the mixture heated to reflux and benzene gradually stripped off. The temperature was then increased to 175C. and maintained for 3.5 hours. After allowing the mixture to cool, equal volumes of both mixed hexanes and 95 per cent ethanol were added and the resulting solution separated into 2 equal portions. One of the portions was allowed to sit in a separatory funnel and the alcoholic phase permitted to separate. The hydrocarbon portion was separated from the alcoholic portion, washed with 10 weight per cent aqueous sodium carbonate, followed by washing with water, and the volatile materials then removed in vacuo. Analysis: wt. nitrogen, 3.03, 3.06; wt. basic nitrogen, 2.26, 2.28.

Example 9 lnto a reaction flask was introduced 600 g. of chloropolyisobutylene (polyisobutylene of approximately 950 molecular weightchlorinated to 5.6 weight per cent), 550 m1. of benzene and 220 g. of alkylene polyamine of the average composition of triethylene tetramine and the mixture allowed to stand at ambient temperatures for 2 days. The benzene was then distilled off, and the temperature of the mixture raised to 150C and maintained for 4 hours. The usual extraction procedure using mixed hexanes and ethanol, followed by sodium carbonate and water washes was carried out and the volatile materials then removed in vacuo. Analysis: wt. nitrogen, 4.10, 4.05; wt. basic nitrogen, 3.07; wt. chlorine, 0.57; molecular wt. (Thermo- NAM), 1,510.

Example 10 Following the procedures of the previous examples, 1,500 g. of chloropolyisobutylene (polyisobutylene of approximately 2,700 molecular weight chlorinated to 6.1 1 weight per cent chlorine) was combined with 350 g. of alkylene polyamine having an average composition of tetraethylene pentamine in one liter of benzene. Analysis: wt. nitrogen, 1.53, 1.53.

Example 11 Following the procedures of the previous examples, 1,423 g. of chloropolyisobutylene (polyisobutylene of approximately 950 average molecular weight chlorinated to approximately 5 weight per cent chlorine) was combined with 286 g. of an alkylene polyamine having an average composition of nonaethylene decamine (DowAmine 400 provided by the Dow Chemical Co.) in 1.4 liters of benzene. Analysis: wt. nitrogen, 4.14, 4.20.

Example 12 r Following the procedure of the previous examples, 600 g. of chloropolyisobutylene (polyisobutylene of ap proximately 2,700 average molecular weight chlorinated to about 2 weight per cent chlorine) was combined with 40 g. of alkylene polyamine having an average composition of tetraethylene pentamine and 540 ml. of benzene. Analysis: wt. nitrogen, 0.99; molecular weight (ThermoNAM), approximately 4,400.

Example 13 lnto a reaction flask was charged 1,156 g. of chloropolyisobutylene (polyisobutylene of approximately 950 molecular weight chlorinated to 7.8 weight per cent chlorine), m1. of xylene and 330 ml. ofethylene diamine, followed by the'addition of 330 ml. of nbutanol. The mixture was then raised to a temperature of C. over one hour and the temperature was then raised to about 160C. and maintained there for about 4 /2 hours. About 330 m1. of distillate was obtained while raising the temperature from to C. The reaction mixture was transferred to a separatory funnel with the aid of one liter of benzene, and the mixture washed repeatedly first with a dilute aqueous solution of isopropyl alcohol, then with a dilute aqueous solution of a combination of isopropyl alcohol and butanol and finally with water. The volatile materials were then removed from a sample of the washed product by sparging with nitrogen to constant weight on a steam plate. Analysis: titrimetric equivalent wt., 806, equal to 1.74 percent nitrogen; wt. chlorine, 0.62.

One thousand four hundred thirty-four g. or about half of the volatile solvents was removed from the main portion of the washed product. This solution containing about 25 percent volatile solvent (titrimetric equivalent weight 1,051) was combined with 240 g. of a mixture of other materials prepared similarly to provide a final product having a titrimetric equivalent weight of 985, the product being polyisobutenyl ethylene diamine.

Example 14 lnto a reaction flask was introduced 1,000 g. of chloropolyisobutene (polyisobutene of approximately 420 molecular weight chlorinated to approximately 8 weight per cent chlorine), 270 ml. of ethylene diamine and 270 ml. of n-butanol. The mixture was heated gradually to 170C. during 1 /2 hours; distillate was collected mainly between 130 and 160C. The mixture was then heated for about 3 hours at 170C. At the end ofthis time, 1,000 ml. of toluene and 250 ml. of methyl isobutyl carbinol were added and the mixture washed with dilute aqueous isopropyl alcohol, followed by repeated washings with water. Some of the volatile solvents were then removed on a steam bath using a nitrogen stream. The combined products from two similar runs were then filtered, yielding 3,91 1 g. Analysis: titrimetric equivalent wt., 840, equal to 1.67,wt. nitrogen. Complete removal of volatile solvents from a small sample indicated the product contains about 40% solvents, i.e.. toluene and methyl isobutyl carbinol.

Example Following the procedure of Example 14, 1,000 g. of chloropolypropylene (polypropylene of about 800 molecular weight chlorinated to about 6 weight per cent chlorine) was reacted with 270 g. of ethylene diamine. The product as finished contained about 15 percent volatile solvents. Analysis: titrimetric equivalent wt., 1,080, equal to 1.3 wt. nitrogen.

Example 16 Following the procedure of Example 6, 1,500 g. of chloropolyisobutylene (polyisobutylene of approximately 950 molecular weight chlorinated to 5.6 weight per cent chlorine) was combined with 285 g. of alkylene polyamine having an average composition of tetraethylene pentamine in 1,200 ml. of benzene. Analysis: wt. 7r nitrogen, 4.15, 4.15: molecular wt. (Thermo- NAM), 1,539.

Example 17 Following the procedure of Example 14, 950 g. of chloropolyisobutylene (polyisobutylene of approximately 950 molecular weight chlorinated to 4.48 weight per cent chlorine) was combined with 270 ml. ofethylene diamine in 270 ml. of n-butanol. The prod-. uct as finished contained about per cent volatile solvents. Analysis: titrimetric equivalent wt., 976, equal to 1.44 wt. nitrogen.

Example 18 Into a high pressure vessel was introduced 1,185 g. of polyisobutenyl chloride (approximately 1,000 molecular weight, wt. chlorine 5.9), 150 g. of ammonia, 500 ml. of benzene and 100 ml. of methanol, the vessel sealed and rocked at 150C. for 13 hours. At the end of this time, the vessel was permitted to cool, the gaseous material vented and the reaction product recovered. The product was extracted with mixed hexanes and alcohol, water being added to aid in the separation of the phases. The volatile materials were then removed in vacuo at elevated temperatures. Analysis: wt. nitrogen, 1.13, 1.14; molecular wt. (ThermoNAM), 1,426.

Example 19 Into a high pressure bomb was introduced 1,200 g. of polyisobutenyl chloride (approximately 500 molecular weight, wt. chlorine -8) and 400 g. of liquid ammonia, the bomb sealed and heated at 150C. with rocking for about 15 hours. After cooling, the pressure was vented and the reaction mixture taken up in mixed hexanes, water and alcohol. The organic phase was then washed with 500 ml. of 5 per cent sodium hydroxide, followed by repeated washings with water. The solvents were then distilled off and the residue, which weighed 767 g., filtered through Celite.

Titration of the product showed an equivalent weight of 1,090, indicating that the material was 40 per cent active (contained 40 per cent by weight of polyisobutenyl amine).

Example 20 Following the procedure of Example 2, 1,100 g. of polypropenyl chloride (approximately 850 molecular weight, wt. chlorine 5.94) was contacted with 400 g. of liquid ammonia. The. product weighed 1,050 g. Titration indicated an equivalent weight of 1,860, indieating 48.4 per cent active.

Example 21 A. lnto a high pressure bomb was charged 1,000 g. of polyisobutenyl chloride (approximately 1,000 molecular weight, wt. chlorine 6), 500 ml. of benzene, g. of methanol and 100 g. of monomethylamine and cooled to 0C. The bomb was sealed and heated to C. and allowed to rock at this temperature for about 24 hours. After allowing the reaction mixture to cool, the mixture was diluted with hexane, filtered and then further diluted with about one-half volume of 95 per cent ethanol. The mixture was then heated to reflux and approximately one-third volume of water added and the aqueous phase separated. After pumping all volatiles from the hydrocarbon phase, the product was isolated. Analysis: wt. nitrogen, 1.01, 1.09; molecular wt. (ThermoNAM), 1,149.

B. Repeating the same reaction under the same conditions with the same amounts of materials, a product was obtained which analyzed: wt. nitrogen, 1.33, 1.30; wt. basic nitrogen, 1.24, 1.27.

Example 22 Into a reaction flask was charged 1,500 ml. of a 75 wt. per cent solution of polyisobutenyl chloride (approximately 1,000 molecular weight, wt. chlorine 5.9) in benzene, 300 g. of ethanolamine and the mixture heated at reflux for -1.5 hours. The benzene was then distilled off and the residue heated at C. for 4 more hours. The reaction mixture was then diluted with an equal volume of hexane and a one-third volume of 95 per cent ethanol and the mixture heated to reflux. To this mixture was then added approximately onethird volume of water, the phases allowed to separate and the organic phase isolated. The volatile materials were then distilled from the organic phase in vacuo. Analysis: wt. nitrogen, 1.01, 1.02; wt. basic nitrogen, 0.98, 0.98.

Example 23 lnto a high pressure bomb was charged 500 g. of polypropenyl chloride (approximately 800 molecular weight, wt. chlorine 5.9), 300 ml. of benzene and 100 g. of liquid ammonia, the mixture cooled to C. and the bomb sealed. The bomb was then heated to 150C. and allowed to rock overnight at that temperature. After allowing the mixture to cool, the mixture was diluted with 1 liter of mixed hexane, the ammonium chloride filtered off and then 800 ml. of alcohol added. After heating the mixture to reflux, water was added to provide phase separation. The hydrocarbon phase was separated, and freed of volatile materials in vacuo. Analysis: wt. nitrogen, 0.96, 0.94; wt. basic nitrogen, 0.65, 0.66.

Example 24 Into a high pressure bomb was introduced 550 g. of a 75 per cent solution of polyisobutenyl chloride (approximately 950 molecular weight, wt. chlorine 5.9) in benzene, 200 g. of dimethylamine, the bomb sealed and the mixture heated at [50C. overnight (approximately l8 hours). After allowing the mixture to cool. it was diluted with mixed hexanes and filtered. To the filtrate was added approximately two-thirds volume of 95 per cent ethanol, the resulting mixture heated to reflux and approximately one-third of volume water then added. After separating the organic phase from the aqueous phase, the volatile materials were removed in vacuo. The product was then analyzed. Analysis: wt. 7! nitrogen, 1.40, 1.42; wt. 76 basic nitrogen, 1.35, l.34.

Example 25 in order to demonstrate the wide applicability of the compounds within the scope of this invention, various compounds were tested under a wide variety of conditions simulating a variety of situations in which lubricating oils are used. Three different engine tests were carried out of varying severity and varying demands on detergents to demonstrate the excellent effectiveness of the compositions of this invention in lubricating oils.

The first test was the Ll Supp. 1 (MlL-L-2l04B, Supp. 1 Specifications). The oil was formulated containing 0.03 weight per cent nitrogen and 8 mM./l g. of 0,0-dialkyl phosphorodithioate (alkyl of from four to. six carbon atoms) in a Mid-Continent SAE 30 base oil. The test was carried out for 120 hours, the following Tested under the less severe L-l conditions (MlL-L-2l04A) "Measured on a rating of 0 to I00, 100 being completely filled "Measured on a rating of 0 to R00. 800 being completely black To further demonstrate the effectiveness as detergents and dispersants of the compositions of this invention, a number of compositions were tested under C aterpillar l-G conditions (MlL-L- 199). To a Mid- Continent SAE 30 base oil was added the detergent and zinc 0,0-di(alkylphenyl) phosphorodithioate (the alkyl is polypropylene of an average of 14 carbon atoms). The test was carried out for hours. The following relnto a pressure vessel was introduced 900 g. of chlo- 35 sults were obtained.

TABLE ll Wt. 7( of Phosphoro- Candidate dithioate Example Detergent mM/kg Grooves" Lands" U.H"

3 676 ts 24-25-002 1355-40 4 4| 12 58-5-0603 5103540 5 4.04 l2 t5-2-0-0 l9l-7-l0 7.0 6 5.25 12 12-3-04) -0-0 7.5 7 4.62 1: 43-4-14 70-0-0 7.5 a 2.90 8 21-5-00 l7t)-5t)-65 7.5 9 1.5 12 |2-2.5-0.2-0.2 -46-25 10 4.80 x 58-3-()-() 15540-5 6.4 it 1.7 l3 69-9.2-2.4-().9 745-420-185 is 6.7 [8 254044 3205040 Base oil 12 934553 5002400470 Rated 0 to l0,

ropolyisobutylene (approximately 2,700 molecular weight, wt. chlorine 5.9), g. of ammonia and 400 g. of benzene, the vessel sealed and heated at 150C. with rocking overnight. The vessel was then allowed to cool, the gas vented, the product mixed with 1 liter of mixed hexanes and the ammonium chloride which precipitated was filtered off. The mixture was then further diluted with about 800 ml. of 95 per cent alcohol. After heating the entire mixture at reflux, water was added and the phases cooled and separated. The hydrocarbon phase was isolated and the volatile materials removed in vacuo. Analysis: wt. nitrogen, 0.4l, 0.42; wt. 70 basic nitrogen, 0.25, 0.21; molecular wt. (ThermoNAM), 3,5l0.

As a further test of the usefulness of the compositions of this invention in lubricating oils, a modified FL-2 test procedure, as described in June 21, 1948 report of the Coordinating Research Council, was employed. This test simulates automobile engine performance. A standard procedure requires the maintenance of a jacket temperature of 95F. and a crankcase oil temperature of F. at 2,500 rpm. and 45 brake horsepower for 40 hours (closely simulating the relatively cold" engine conditions which are normally experienced in city driving). At the end of each test, the engine is dismantled and the amount of total sludge (rating of 0 to 50, no sludge being 50) and clogging of the rings and oil screen (rating ofO to 100, no clogging being 0) is determined. Also, the piston varnish is rated (rating of 0 to 1'7 l8 10, no varnish being 10) and the total varnish is evaluthe finished oil contained 0.126 weight per cent nitroated (rating of to 50, no varnish being 50 The gen. above test was modified by increasing the time and pe- The Yamaha engine test uses a 75 cc. Model YG-l riodically raising the oil sump temperature from 165F. motorcycle engine. The same conditions as described to 205F. and the water jacket temperature from 95 t for the McCulloch engine are also used for the Yamaha 170}; engine.

Using a Mid-Continent SAE 30 b k, h The following table indicates the results obtained with a variety of detergents in the McCulloch engine didate detergent was employed at concentrations to and m the Yamaha engine tests.

provide a constant weight per cent of nitrogen; also in- TABLE IV Wt. 71 in oil of Ring Candidate F Sticking 6.0. No. Land Dep. Exh. Piston Total Example Detergent V Top 2nd Top 2nd Top 2nd Ports Und. Rating McCULLOCH 5 7 9.2 360 F 6 500 250 5 8.3 37.0 6 9 7.5 360 F 700 640 7 7.8 30.8 l8 ll.l 9.4 F F 2 l 750 600 7 8.7 38.7 19 ll 7.7 360 F ll 750 550 7 7.2 30.5 21A l2 9.7 I80 F l 450 240 6 9.3 41.5 22 12.5 7.3 360 F 5 680 3l() 7 9.1 34.3 24 8.9 7.9 360 F 5 740 680 12 7.8 30.4 25 8. l 360 F 3 650 420 5 6.4 32.l Base Oil 6.4 360 F 5 580 (alt) l0 6.0 28.7

YAMAHA 5 7 8.6 360 F I0 640 620 I2 6.2 30.2 ltt ll.l 9.0 360 F 4 720 480 I5 4.7 29.5 2|B 9.2 9.2 360 F 4 750 560 22 5.4 29.0 Base Oil (1.0 360 I60 700 750 I5 l.4 l9.6

PV piston varnish *G.D.No. groove deposit nI-Imher Land Dep. land deposit number 'Exh. Ports exhaust ports Piston Und. piston underhead cluded in the oil was 10 mM./kg. of zinc 0,0-dt(alkyl) The data graphically demonstrate the wide range of dithiophosphate (alkyl of from four to six carbon applicability of the compositions of this invention. The atoms) and 2 mM./kg. of zinc 0.0-di(alkylphenyl) diexcellent detergent and dispersant results are obtained thiophosphate (alkyl is polypropylene of from l2 to 15 under a wide variety of conditions in a wide variety of carbon atoms).The following table indicates the results engines. Despite the relative simplicity of the moleobtained. I cules, as compared to the wide variety of detergents TABLE Ill Wt 7p of Candidate Piston Total Total Clogging Time Example Detergent Varnish Varnish Sludging Ring Screen Hr.

4 0.98 3.5 If) 35 27 2O 80 6 3.50 4.3 23 48 2 4 I00 7 2.64 4.5 14 37 25 3 I00 8 L44 4.] 23 4I 18 I0 I00 II! 4.35 4.3 17 49 O l 100 Base Oil Engine stopped in approximately I2 hours The results demonstrate that the branched chain hythat have preceded them, the compositions of this indrocarbon substituted polyamines provide excellent vention are able to function in lubricating oils under seversatility in providing detergency and dispersancy vere field conditions-the hot diesel engine, the variunder broad variations in conditions and varying enable temperature stop-and-go automobile engine, and g nc r quiremen the 2-cycle engine. Moreover, the compounds are Turning now to a consideration of the use of the dereadily available by simple synthetic methods, provide tergents and dispersants of this invention in oils to be detergency without producing ash and either do no or Used in y Spark ignliio" engines- TWO different only to an insignificant degree create deposits from engines were used: a Yamaha engine which used on h i Own decomposition products motorcycles and a McCulloch engine whic is used for As will be evident to those skilled in the art, various chum saws modifications on this invention can be made or foli c f l 2 52 3% 2??? lowed, in the light of the foregoing disclosure and dis carric d di ft i i i li ours t he e ri iii ti i run it 7 00: cuSSlO-n without departing from the Spmt or scopeof r p m ,natempemmre and witghawide p the disclosure or from the scope of the following throttle. Using regular gasoline. a fuel-oil mixture in the Claims ratio of 20:1 is prepared, the oil composition being a We claim:

blend of detergent in SAE 40 grade base oil, such that l. A composition of the formula:

A is hydrogen or hydrocarbyl of from 1 to 10 carbon atoms, 1

Z is hydrogen, or hydrocarbyl of from one to 10 carbon atoms, and may be taken together with A to form a ring with the nitrogen to which A and Z are attached consisting of from 5 to 6 annular members having from to 1 oxygen annular memher, 1 nitrogen annular member and 4 to 5 carbon annular members.

2. A composition according to claim 1,

wherein A and Z are hydrogen or alkyl of from one to six carbon atoms.

3. A lubricating oil composition having in an amount sufficient to provide detergency and dispersancy, a composition according to claim 1.

v 4. A lubricating oil composition according to claim 3, having from I to 50 mM./kg. of a zinc phosphorodithioate.

5. A composition accoding to claim 1 wherein R is a branched chain aliphatic hydrocarbon radical derived from polymerizing olefins of from three to six carbon atoms.

6. A composition according to claim 1 wherein R is polyisobutylene.

7. A composition according to claim l wherein R is polypropylene or polyisobutylene.

8. A compound of the formula where R is a branched chain hydrocarbon radical having a molecular weight of from about 425 to about 3,000 and R, and R are selected from the group consisting of hydrocarbon radicals having from one to about carbon atoms and hydrogen.

9. A compound of the formula where R is a branched chain hydrocarbon radical having a molecular weight of from about 425 to about 3,000. 1

10. A compound of the formula where R is a branched chain hydrocarbon radical having a molecular weight of from about 425 to about 3,000.,

ll. A lubricant composition comprising a major amount of a lubricating oil and a minor amount of a compound of the formula Gib-CH2 where R is a hydrocarbon radical having a molecular weight of from about 425 to about 3,000.

13. A lubricant composition comprising a major amount of a lubricating oil and a minor amount of a comp- "nd of the formula where R is a hydrocarbon radical having a molecular weight of from about 425 to about 3,000.

Claims

1. A COMPOSITION OF THE FORMULA:

2. A composition according to claim 1, wherein A1 and Z1 are hydrogen or alkyl of from one to six carbon atoms.

4. A lubricating oil composition according to claim 3, having from 1 to 50 mM./kg. of a zinc phosphorodithioate.

6. A composition according to claim 1 wherein R is polyisobutylene.

7. A composition according to claim 1 wherein R is polypropylene or polyisobutylene.

8. A compound of the formula

9. A compound of the formula

10. A compound of the formula

11. A lubricant composition comprising a major amount of a lubricating oil and a minor amount of a compound of the formula

12. A lubricant composition comprising a major amount of a lubricating oil and a minor amount of a compound of the formula

13. A lubricant composition comprising a major amount of a lubricating oil and a minor amount of a compound of the formula