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Publication numberUS3455832 A
Publication typeGrant
Publication dateJul 15, 1969
Filing dateSep 9, 1963
Priority dateSep 9, 1963
Also published asDE1594486A1, DE1594486B2, US3453832
Publication numberUS 3455832 A, US 3455832A, US-A-3455832, US3455832 A, US3455832A
InventorsJames B Davis
Original AssigneeMonsanto Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Schiff bases
US 3455832 A
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Description  (OCR text may contain errors)

United States Patent 3,455,832 SCHIFF BASES James B. Davis, Kirkwood, Mo., assignor to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed Sept. 9, 1963, Ser. No. 307,329 Int. Cl. Cm 1/32 U.S. Cl. 25251.5 23 Claims ABSTRACT OF THE DISCLOSURE Compounds useful as detergents in lubricating oil com- 10 positions represented by the structure 3,455,832 Patented July 15, 1969 in which R is a polyalkenyl radical having an average molecular weight of from about 500 to about 2500; R is selected from the group consisting of a phenyl, a naphthyl and a furfuryl radical; R is selected from the group consisting of hydrogen, an alkyl radical containing from one to twenty carbon atoms, a phenyl, a naphthyl and a furfuryl radical; R is selected from the group consisting of hydrogen and alkyl radicals having from one to three carbon atoms, m is a whole number from Zero to three, and y is a whole number from one to four.

This invention relates to new Schiif bases and related materials useful as detergents in lubricating oil compositions.

Under the conditions encountered in a large percentage of present-day automobile driving (i.e., the so-called stopand-go driving), automobile engines do not attain their most desirable and efiicient operating temperatures. As a result, large quantities of undesirable products are formed which eventually find their way into the crankcase Where they tend to deposit on the internal parts of the engine resulting in further inefiicient engine operation. In presentday practice, deposition of such products is minimized by incorporating into lubricating oils metal-containing detergents. The use of metal-containing detergents may, however, form ash deposits in the combustion chambers of engines, fouling the spark plugs and creating other problems and, accordingly, it is the desire of those working in the art to find suitable detergents which are metalfree or ashless.

It has now been found that certain Schiif bases or arylidene amines are useful as metal-free or ashless detergents in lubricating oil compositions and especially where such compositions are used at relatively low engine temperatures. The amines which are the subject of the present invention can be represented by the structure where R is a polyalkenyl radical having a molecular weight of from about 500 to about 2500, preferably about CHz-lcl or the acid thereof, with (b) A polyamine represented by the structure NHr-[CHz-?H(OH2)mNH] -CHa?H(CHz)m- 1 Ra Ra to produce an intermediate product, an imide (which is a polyalkenylsuccinirnidoazaalkylarnine), represented by the structure 1? R-CH-C N[CH -(I3H(CHz)mNH] CH -(H(CH2)mHN CHr-(HD R3 R3 which is in turn reacted with (c) A carbonyl-containing aromatic or heterocyclic compound represented by the structure thereof, having a. molecular weight of from about 500 to about 2500, but preferably about 800 to about 1500. The

preparation of the polyalkenylsuccinic anhydrides is best elfected at temperatures of the order of about 150 C. to 250 C. by reacting maleic anhydride with the olefin polymer in mol ratios of from 1:1 to about :1, respectively. Since the reaction between the olefin and maleic anhydride may not go to completion, the resulting polyalkenylsuccinic anhydride can contain some unreacted olefin which can be allowed to remain as a diluent with no harmful effects upon the performance of the compounds of this invention.

The polyamines useful in preparing the Schifi bases of the present invention are azaalkyleneamines which are available commercially, but which can also be prepared from alkylene dichlorides and ammonia. Examples of such amines are 'diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentam'ine, pentaethylenehexamine, and the like.

As is evident from the description of the compounds of this invention the carbonyl-containing compound can be an aldehyde or ketone. The aldehydes useful in preparing the Schilf bases of this invention can be of an aromatic or heterocyclic nature. Representative examples of such aldehydes where R is a phenyl radical and R is hydrogen are benzaldehyde; alkyl-substituted benzaldehyde, e.g., 2-, 3- and 4-methylbenzaldehyde, 2,6- and 3,5-dimethyl-benzaldehyde, 2-, 3- and 4-ethylbenzaldehyde, 4- isopropylbenzaldehyde, Z-isobutylbenzaldehyde; 4-octylbenzaldehyde, 2,3,6 and 2,4,5 trimet-hylbenzaldehyde, 2,3,5,6 tetrarnethylbenzaldehyde; 2 hydroxy 5 methylbenzaldehyde; halogen-substituted benzaldehyde, e.g., Z-fiuorobenzaldehyde, 2-, 3- and 4-chlorobenzaldehyde, 2-, 3- and 4-bromobenzaldehyde, 2-iodobenzaldehyde, 3,4 diechlorobenzaldehyde, 2,3,5 trichlorobenzaldehyde, pentachlorobenzaldehyde, 2-trifiuoromethyl benzaldehyde; alkoxy-substituted benzaldehyde, e.g., *2- and 3-methoxybenzaldehyde, 4-methoxybenzaldehyde (anisaldehyde), 2-, 3- and 4-ethoxybenzaldehyde, 2,3- and 3,4- dimethoxybenzaldehyde, 4 hydroxy 3 methoxybenzaldehyde (vanillin), 3 ethoxy 4 hydroxybenzaldehyde, 3,4,5-tnimethoxybenzaldehyde, 4-methoxy-3-hydroxybenzaldheyde (iso-vanillin); hydroxy-substituted 'benzaldehyde, e.g., Z-hydroxybenzaldehyde (salicylaldehyde), 4- hydroxybenzaldehyde, 2 hydroxy 4 chlorobenzaldehyde, 2-ethyl-4-hydroxybenzaldehyde, 2,6- and 3,5-dihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde. Other substituents can include nitro, as in Z-nitrobenzaldehyde; amino, as in Z-aminobenzaldehyde and 4-diethylaminobenzaldehyde; benzyloxy, as in 3-benzyloxybenzaldehyde; carboxyl, as in benzal-dehyde-Z-carboxylic acid and 2- hydroxybenzaldehyde-3-carboxylic acid; phenoxy, as in 2-phenoxybenzaldehyde; vinyl, as in 2-vinylbenzaldehyde; and cyano, as in Z-cyanobenzaldehyde.

In the case where R is a naphthyl radical and R is hydrogen typical starting aldehydes are for example 1- and Z-naphthaldehyde, 4-methoxy-l-naphthaldehyde, 1- hydroxy 2 naphthaldehyde, 4 phenyl 2 naphthaldehyde, and the like. Where R is a furfuryl radical and R is hydrogen starting aldehydes include 2- and 3-furfuraldehyde, S-methylfurfuraldehyde, 5-hydroxy-2-furfuraldehyde, and the like.

When R is not hydrogen the carbonyl-containing aromatic or heterocyclic compound is a ketone, which can be of an aromatic, heterocyclic or mixed structure.

The ketones useful in preparing the Schifl [bases of this invention are represented by the following non-limiting examples: acetophenone, propionphenone, butyrophenone, pelargonophenone, capriphenone, hendecanophenone, acetonapthone, capronapthone, arachidophenone, stearonapthone, benzoin, methyl-2-naphthyl ketone, benzophenone, 4,4-bis(dimethylamino)benzophenone, 4- methyl benzophenone, 4,4-dimet-hyl benzophenone, 2-, 3- and 4-hydroxy benzophenone, 4,4'-dihydroxy benzophenone, l-naphthyl ketone, 4-methyl-l-naphthyl l-naphthyl ketone, 4 methoxy 1 naphthyl l naphthyl ketone, 4

amino-l-naphthyl l-naphthyl ketone, l-naphthyl phenyl ketone, furfuryl ketone, methyl furfuryl ketone, phenyl furfuryl ketone, l-naphthyl furfuryl ketone.

The intermediate imides described above can be prepared by heating a toluene or other hydrocarbon solution of a polyalkenylsuccinic anhydride and a polyamine at temperatures of the order of about 50 C. to about 200 C., using mol ratios of anhydride to polyamine of about 1:1 while at the same time continuously removing the Water formed from the reaction. Typical examples of the imides used to prepare the Schifi bases of this invention are given below. In naming the imides and Schifi. bases herein, the approximate molecular weight of the polyalkenyl chain is denoted by the number in parentheses after the name of the polyalkenyl group in a particular compound.

5- [polypropenyl 900 succinimido] -3-azapentylamine,

7- [polyethenyl( 1200) succinimido] -4-azaheptylamine,

8- [polyethenyl 1 500) succinimido] -3,6-diazaoctylamine,

9- polypropenyl( l 800) succinimido] -5-azanonylamine,

9- [polybutenyl (900 succinimido] -5azanonylamine,

8- [polybutenyl (980)succinimido] -3,6-diazaoctylamine,

1 1- [polybutenyl 135 0)succinimido] -3,6,9-triazaundecylamine,

11- [polypr0penyl'(980) succinimido] -3,6,9-triazaundecylamine.

The imides, as described above, are then reacted with a carbonyl-containing aromatic or heterocyclic compound while continuously removing the water formed from the reaction to provide the Schifi bases of this invention. To provide a reaction medium and to facilitate the removal of the water of reaction, the preparation of the present Schiff bases is generally carried out in a hydrocarbon solvent, e.g., toluene or xylene. Likewise the preparation of the Schilf bases of the present invention can be carried out in a mineral oil solution or dispersion or the mineral oil can the used in combination with a hydrocarbon solvent. Suitable temperatures for preparing the Schiif bases of the present invention at atmospheric pressure are of the order of 50 C. to 200 C.

Typical examples of the Schiff bases of this invention are:

N-naphthylpropylmethylene-S-polypropenyl 1200) succinimido-3-azapentylamine, N-naphthylphenylmethylene-7-polybutenyl 1 succ1mm1do-4-azaheptylamine, and the like.

The preparation of the Schilr bases of this invention is lllustrated in the following non-limiting detailed examples, wherem parts are parts by weight unless otherwise stated.

Example 1 Into a suitable reaction vessel fitted with a mechanical stirrer, heating mantle, thermometer, Dean-Stark trap and condenser, containing 200 ml. of toluene and 74.3 parts of diethylenetriamine, there were charged 917 parts of polybutenyl(980)succinic anhydride. An additional 200 ml. of toluene containing a catalytic amount of p-toluenesulfonic acid was charged and the resulting mixture was then heated, with stirring, to reflux and maintained at reflux until the evolution and collection of water ceased. The reaction mixture was then cooled to about 70 C., 76.4 parts of benzaldehyde were charged, and heating at reflux was continued until the evolution and collection of water ceased. The toluene was then stripped under vac- In a similar manner the other Schifif bases contemplated by this invention can be prepared.

The Schiif bases of this invention can be used in lubricating oils in amounts of from about 0.05% to about 25% by weight. Additive concentrates of 60-95% are also contemplated. It has been found, however, that in finished formulations, for most applications, amounts of from about 0.25% to about 10% by weight are sufficient. In addition, the compounds of this invention can be used in fuel oils and in various light products, such as gasoline, wherein they also function as detergents or dispersants.

A screening test was utilized to demonstrate the detergency effectiveness in gasoline engine oil formulations of uum to leave 1052 parts of N-benzylidene-S-polybutenyl thischifi bases of t i f p' This test ria'fen'ed as (980)succinimido 3 azapentylamine, which analyzed a .Ifacquer Deposltlon test, IIIVOIVES paesmg partially 2 72% nitrogen and had a base number of 108 oxidized gasoline through a sample of an oil formulation in a suitable container under controlled conditions, after Example 2 which the sample is aged in an oven. The amount of de- In the manner of Example 1, 148 parts of polybutenylposit is then determined by washing away the oil. A con- (1315 )succinic anhydride and 8.9 parts of diethyleneformulatlon 13 T1111 slmultaheohslyz The g r I6- triamine in toluene were heated to reflux and stirred until Ported TBPYCSFMS the Percent Tedllchon 1n d posits when the evolution and collection of water ceased. The resulta detfargent 15 Present P t0 t e ount of ing imide was then reacted with 9.1 parts of benzaldehyde deposlt when 110 detergent 18 p e e great advantage and reflux was continued until the collection of water 2 of the Lacquer DBPOSIUOH Test 18 t e results obtained ceasecl The tomene was removed to give 5 parts of correlate well with the results which are obtained in low N benzylidene 5 polybutenyu1315)succinimido temperature gasoline engine tests such as the Lincoln MS azapentylamine which analyzed 7% nitrogen with a Test. Utilizing the above described test, the results prebase number f 5 sented 111 Table II, below, were obtained using a con- Example 3 centration of 2% by Weight of the Schilf base tested. In the manner of Example 1, 230 parts of polybutenyl- T B 11 (980)succinic anhydride and 25.2 parts of triethylene- Test Schfib L 4 tetrainine in 120 ml. of toluene were heated to reflux un- 1 ass acquer deposltm til the evolution and collection of water ceased. Upon g:

--- a; cooling, 18.3 parts of benzaldehyde were added and then 3 I Example 3:: s3 reflux was continued until the further collection of water Examplei 96 had ceased. The toluene was stripped to give 268 parts of N benzylidene 8 polybutenyl(980)succinimido 3, From the above, it is clear that the addition to lubri- 6-diazaoctylamine. cating oils of the Schiff bases of the present invention Example 4 brings with it a clear improvement of the dispersing In the manner of Example 1, 150 parts of polybutenyb and/or detergent qualities of said oils. Nevertheless the (ggmsuccinic anhydride and 221 parts of tetraethy1ene greater part of the commercial lubricating oils sold today pentamine in toluene were heated to reflux and Stirmd are SllbJGCt to a large number of uses, and it is, therefore, until the evolution and collection of water ceased. Upon s e r r to 12 3 more i one yp of cooling, 12.4 parts of benzaldehyde were added and then addltlve a fimshed lubncant cfimlposltloh- Thus, reflux was continued until further evolution and c01]ec though the products of the present invention are effective tion of water had ceased. The toluene was removed to f f 15 frefluenfly necessary to sjlch P s give 178 parts ofN-benzylidene-12-polybutenyl(980 succomblna'tlflm Wlth other yp addltlves, aS cinimido-3,6,9-triazadecylamine which analyzed 4.6% fnetaljcontamlhg f f h j and/01 dlspersalltsi COYTOSIOH nitrogm with a base number f 2 0 inhibitors, oxidation inhibitors, extreme pressure agents,

Additional examples of other Schiff bases of this inven- FY mdex p f P -P depressor?! tion and the materials used for their preparation are given foamlng Qg and The 0 in Table I, bel w, I th t bl l h alkenyl l A particularly useful combination of additive 1ntended alkenyl, portion of the polyalkenylsuccinic anhydride and to beapplied in motor lubricants is the combination ofan the average molecular weight of such portion are given, additive 0f t Presfiht mvehhoh and a metal-contalhmg DETA means diethylenetriamine, TETA means triethylderivative of phosphorus such as a metal phosphorodienetetramine and TEPA means tetraethylenepentamine. thioate, e.g., zinc dihexyl phosphorodithioate, the zinc TABLE I Alkenyl portion of alkenylsuccinic anhydride Polyethylene Carbonyl-containing Molar ratio E 1 (mol wt. of alkenyl group) amine compound ii e (a) (b) (c) (a):(b):(c) Product 1:111 N-B- iii tii lb l'd 3,6-d h -1 5-.- Polybutenyl (980) DETA Acetophenone p g g g ya g g g1 l s l e ne iaza ex y 6 do TETA Benzophenone 1:1:1 N-[9-diphenylmethylene-3,6,9-triazanonyl]- 1 N ii li 3 6 9 1" 1:1: y 7 o y ny fl TEPA N p y p opy temazlgdodecympolybutenyl(1350* i 1 N ii iiiii iidenes s 9 i2 tetraazadodec 11 1: ur 8 o y e y 8 A. u polybutensgl(gsmsuccimmide. y 9 Polybutenyl (1350) TE'IA Naphthaldehyde 1:1:1 N-[9-riaphthy1idene-3,6,9:triazadodecyl]- polybutenyl(1350)succiri1mide. 10 Polybutenyl (980) 'IEPA Vanillin 1:121 N-[12rvanillylidene-3,6,Q,12t etraazadodecy1]- polybutenyl(980)suc c1nimide. 11 Polybutenyl (1350) DETA Salicylaldehyde 1 N-[Frsalicy1idene-3fi-diazahexyl]polybuteny1- (1350) succinimide.

salt of mixed alkyl phosphorodithioates where the alkyl groups are obtained, for example, from an equal mixture of isobutyl and n-arnyl alcohols, and the metal salts of phosphorus sulfide-olefin polymer reaction products and combinations thereof.

Lubricating oils which can be used as the base oils to which the new compounds of this invention are added are not limited as far as detergent effects are concerned, and, accordingly, can be lubricating oils which are of a naphthenic base, paraffinic base, and other hydrocarbon bases, as well as lubricating oils derived from coal products and synthetic oils, such as alkylene polymers, alkylene oxide polymers, dicarboxylic acid esters, alkylated benzenes, silicate esters, silicon polymers, and the like, are suitable.

In addition to the above, it has been found that by utilizing the same reactants as are used to prepare the Schiff bases of the present invention, but in molar ratios other than about 1:1:1, products can be prepared which also exhibit outstanding detergent properties. Thus, it has been found that by interacting (a) a polyalkenylsuccinic anhydride, (b) a polyamine, and (c) a carbonylcontaining aromatic or hetrocyclic compound, as aforedescribed, in mol ratios of (b):(c) of from about 1:0.75 to 1:12, preferably about 1: 1, and mol ratios of (a) (b) of from above 1:1, respectively, to about 1.621, respectively, preferably from about 1.1:1 to 1.411, respectively, reaction products are formed whose structure is unknown, but which can be used as ashless detergent additives in all types of lubricating oils.

The amount of excess polyalkenylsuccinic anhydride used (relative to the polyamine) is important since large excesses above about 60% tend to reduce the advantageous qualities of the products. Accordingly, the amount of excess polyalkenylsuccinic anhydride should range from more than to about 60%. Engine test experience with the various products encompassed by this part of our invention has shown that the amount of such excess is preferably from about 10% to about 40%.

The amount of excess or deficiency of carbonyl-containing compound (relative to the polyamine) can vary from a mol ratio of 1:1.2 to 1:0.75, respectively, as mentioned above. However, mol ratios of about 1:1 are preferred since a loss of detergency is experienced at ratios significantly different than 1:1 and, beyond the range of ratios mentioned, the resulting products are commercially unsatisfactory detergents.

To provide a reaction medium and to facilitate the removal of the water of the reaction, a hydrocarbon solvent or mineral oil or combination thereof can be used as more fully described with reference to the preparation of the Schiff bases. Suitable temperatures for preparing the reaction products at atmospheric pressure are on the order of 50 C. to 200 C., preferably from 80 C. to 150 C.

The preparation of products using (a) a polyalkenylsuccinic anhydride, ('b) a polyamine and (c) a carbonylcontaining aromatic or heterocylic compound in various mol ratios is illustrated in the following non-limiting examples wherein parts are parts by weight. The raw materials (a), (b) and (c) can be reacted in indifferent order, and in portions, if desired. In carrying out the reaction refluxing of reactants is always continued until the formation of by-product water is complete or essentially complete.

Example 12 In this example the mol ratio of reactants (a) (b) :(c) was 1.2: 1: 1, respectively.

Into a suitable reaction vessel, fitted as previously described, and containing 26.3 parts of tetraethylenepentamine (0.1387 mol) in toluene, there was charged 7.36 parts of benzaldehyde (0.0693 mol). A slight temperature rise was noted. Then 287 parts of polybutenylsuccinic anhydride in toluene was slowly added (the average molecular weight of the alkenyl group was 1315 and therefore 0.1665 mol was added). Again some heat evolution was noted. After completing the anhydride addition, an additional 7.36 parts of benzaldehyde were charged and the resulting mixture was then heated at reflux (about 125 C.) for about three hours while continuously removing water formed in the reaction.

The reaction system Was then placed under vacuum and the toluene stripped (maximum temperature was about 150 C.) to leave 324 parts of product which analyzed 1.73% nitrogen and had a base number of 1.28.

Example 13 In this example the reactants were the same as in Example 12, but the mol ratio of (a):(b):(c) was changed to 1.1 1: 1, respectively.

Into the reaction vessel containing 32.85 parts of tetraethylenepentamine (0.1737 mol) in toluene was slowly added 9.2 parts of benzaldehyde (0.0868 mol) followed by a slow addition of 285 parts of polybutenylsuccinic anhydride (the average molecular weight of the alkenyl group was 980 and therefore 0.191 mol was added) in toluene. Finally, another 9.2 parts of benzaldehyde (0.0868 mol) was added before refluxingfor three hours with water being removed as it formed from the reaction. After the removal of toluene there remained 330 parts of product which analyzed 3.04% nitrogen and had a base number of 1.90.

Example 14 In this example the mol ratio of (a):(b):(c) was 1.2: l 1, respectively.

Into the reaction vessel containing 32.2 parts of tetraethylenepentamine (0.1704 mol) in toluene was slowly added 9.0 parts benzaldehyde (0.0852 mol). Next 280 parts of polybutenyl(980)succinic anhydride (0.2042 mol) in toluene was slowly charged. Finally, another 9.0 parts of benzaldehyde was slowly added. The reaction mixture was refluxed for three hours with water being continuously removed as it formed. Thereafter the toluene was stripped to leave 323 parts product which analyzed 2.39% nitrogen with a base number of 1.70.

Example 15 In this example the mol ratio of reactants (a) :(b) (c) was 1.2 1 1, respectively.

Into a suitable reaction vessel, fitted as previously described, and containing 13.98 parts of tetraethylenepentamine (0.0738 mol) in ml. of toluene, there was added dropwise 9.1 parts of salicylaldehyde (0.0738 mol). To this yellow-colored mixture was then added a solution of 150 parts of polybutenyl-(1368)succinic anhydride (0.0885 mol) and ml. of toluene. The reaction mixture was then refluxed for about three hours while the by-product water which evolved was collected. When the evolution and collection of water ceased, the toluene was removed under vacuum to give 172 parts of product which analyzed 1.79% nitrogen with a base number of 0.91.

The reaction products prepared above were then tested to substantiate their utility as detergents. The Lacquer Deposition Test which was previously described was used for this evaluation.

The reaction products disclosed therein can be used in lubricating oils in amounts of from about 0.05% to about 25% by weight. Additive concentrates of 6095% are also contemplated. It has been found, however, that in finished formulations, for most applications, amounts of from about 0.25% to about 10% by weightare suflicient. In addition, the reaction products of this invention can be used in fuel oils and in various light products, such as gasoline, wherein they also function as detergents or dispersants.

The Lacquer Deposition Test results obtained with the products of Examples 12-15, all at 1% concentration, were as follows:

9 TABLE III LDT,

Additive: percent reduction Product of Example 12 99 Product of Example 13 63 Product of Example 14 94 Product of Example 15 98 From the above, it is clear that the addition to lubricating oils of the reaction products described herein brings with it a clear improvement of the dispersing and/or detergent qualities of said oils. Nevertheless the greater part of the commercial oils sold today are subject to a large number of uses, and it is, therefore, generally necessary to employ more than one type of additive in a finished lubricant composition. Thus, although the reaction products prepared above are effective detergents, it is frequently necessary to use such products in combination with other types of additives, such as metal-containing detergents and/ or dispersants, corrosion inhibitors, oxidation inhibitors, extreme pressure agents, viscosity index improvers, pour-point depressors, antifoaming agents, and the like.

The lubricating oils which can be used as the base oils to which the reaction products disclosed herein are added are not limited as far as detergent effects are concerned, and, accordingly, can be the lubricating oils heretofore described.

While this invention has been described with reference to various specific examples and embodiments, it is understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound represented by the structure 10 8. The product prepared by the interaction, at temperatures of the order of 50 C. to 200 C., of

(a) a polyalkenylsuccinic anhydride in which the polyalkenyl group has an average molecular weight of from about 500 to about 2500; (b) a polyamine, represented by the structure in which R is selected from the group consisting of hydrogen and alkyl radicals having from one to three carbon atoms, m is a whole number from zero to three, and y is a Whole number from one to four; and

(c) a carbonyl-containing aromatic or heterocyclic compound represented by the structure where R is selected from the group consisting of a phenyl, naphthyl and a furfuryl radical; R is selected from the group consisting of hydrogen, an alkyl radical containing from one to twenty carbon atoms, hy-

drogen, a phenyl, a naphthyl and a furfuryl radical,

the mol ratio of (a):(b) being from above 1:1 to about 1.6:1, respectively, and the mol ratio of (b):(c) being from about 1:0.75 to about 1:12, respectively.

9. The product prepared by the interaction at temperatures of the order of 50 C. to 200 C., of

(a) a polybutenylsuccinic anhydride in which the polybutenyl group has an average molecular Weight of from about 800 to about 1500;

(b) a polyamine, represented by the structure NH [CHz(]3H(CHz)m-NH] OH -(fH(OHz)mNH a Rs in which R is selected from the group consisting of in which R is a polyalkenyl radical having an average molecular Weight of from about 500 to about 2500; R is selected from the group consisting of a phenyl, a naphthyl and a furfuryl radical; R is selected from the group consisting of hydrogen, an alkyl radical containing from one to twenty carbon atoms, a phenyl, a naphthyl and a furfuryl radical; R is selected from the group consisting of hydrogen and alkyl radicals having from one to three carbon atoms, m is a whole number from zero to three, and y is a whole number from one to four.

2. A compound of claim 1 where R is polybutenyl of an average molecular Weight of from about 800 to about 1500.

3. A compound of claim 1 where R is polybutenyl of an average molecular weight of from about 800 to about 1500, R is hydrogen, R is hydrogen and m is zero.

4. A compound of claim 1 where R is polybutenyl of an average molecular weight of from 800 to about 1500, R is phenyl, R is hydrogen, R is hydrogen and m is zero.

5. N-benzylidene-5-polybutenylsuccinimido-3-azapentylamine in which the polybutenyl group has an average molecular weight of about 1300.

6. N-benzylidene l1 polybutenylsuccinimido-3,6,9-triazaundecylamine in which the polybutenyl group has an average molecular weight of about 1000.

7. N benzylidene l1 polybutenylsuccinimido-3,6,9- triazaundecylamine in which the polybutenyl group has an average molecular weight of about 1300.

hydrogen and alkyl radicals having from one to three carbon atoms, m is a whole number from zero to three, and y is a Whole number from one to four; and

(c) a carbonyl-containing aromatic or heterocyclic compound represented by the structure Where R is selected from the group consisting of a phenyl, a naphthyl and a furfuryl radical; R is selected from the group consisting of hydrogen, an alkyl radical containing from one to twenty carbon atoms, a phenyl, a naphthyl and furfuryl radical. the mol ratio of (a) (b) being from about 1.1:1 to about 1.421, respectively, and the mol ratio of (b):(c) being about 1 1, respectively.

10. The product prepared by the interaction at temper- 65 atures of the order of C. to 200 C., of

(a) a polybutenylsuccinic anhydride in which the polybutenyl group has an average molecular weight of from about 800 to about 1500; (b) a polyamine, represented by the structure NHg-[CHg-(|)H(CH )mNH] -CHZ(EH(CH2)m NHg in which R is hydrogen, m is zero and y is a Whole number from one to four; and

(c) a carbonyl-containing aromatic or hetrocyclic compound represented by the structure R,( i-R where R is selected from the group consisting of a phenyl, a naphthyl and a furfuryl radical and R is hydrogen, the mol ratio of (a):(b):(c) being from about 1.1 to 1.4:111, respectively.

11. The product prepared by the interaction at temperatures of the order of 50 C. to 200 C., of

(a) a polybutenylsuccinic anhydride in which the polybutenyl group has an average molecular Weight of from about 800 to about 1500;

(b) tetraethylenepentamine; and

(c) benzaldehyde, the mol ratio of (a):(b):(c) being from about 1.1 to l.4:1:1, respectively.

12. The product prepared by the interaction, at temperatures of the order of 50 C. to 200 C., of

(a) a polybutenylsuccinic anhydride in which the polybutenyl group has an average molecular weight of 1300;

(b) tetraethylenepentamine; and

(c) benzaldehyde, the mol ratio of (a):(b):(c) being from about 1.2:1:1, respectively.

13. A composition comprising a major amount of a lubricating oil and from about 0.05% to about 25% by weight of a compound of claim 1.

14. A composition comprising a major amount of a lubricating oil and from about 0.05% to about 25% by Weight of a compound of claim 4.

15. A composition comprising a major amount of a lubricating oil and from about 0.05% to about 25% by weight of a compound of claim 6.

16. A composition comprising a major amount of a lubricating oil and from about 0.05 to about 25 by weight of a compound of claim 7.

17. A composition comprising a major amount of a lubricating oil and from about 0.05% to about 25% by weight of a product of claim 8.

18. A composition comprising a major amount of a lubricating oil and from about 0.05 to about 25 by weight of a product of claim 11.

19. A composition comprising a major amount of a lubricating oil and from about 0.05 to about 25 by weight of a product of claim 12.

20. A compound having the structural formula:

RCH (J Rt N(CH2CHzNH) CH CH N=C CHz-C R2 where R is a polyalkenyl group having a molecular weight of about 940, y isa whole number from 1 to 3, R is phenyl and R is selected from the group consisting of hydrogen, alkyl and phenyl.

21. A composition which comprises a major amount of a substance selected from the group consisting of lubricating oils and normally liquid hydrocarbon fuels and a minor amount, sufiicient to impart dispersancy, of a compound having the structural formula:

where R is a polyalkenyl group having a molecular weight of about 940, y is a whole number from 1 to 3, R is phenyl and R is selected from the group consisting of hydrogen, alkyl and phenyl.

22. A compound having the structural formula:

Where R is a polyalkenyl group having a molecular weight of from about 500 to about 1800, y is a whole number from 1-3, R is phenyl and R is selected from the group consisting of hydrogen, alkyl and phenyl.

References Cited UNITED STATES PATENTS 3,131,150 4/1964 Stuart et a1. 252-51.5 2,279,561 4/1942 Dietrich 25250 2,409,799 10/1946 Roberts 25250 X 3,131,150 4/1964 Stuart et a1. 25251.5

PATRICK P. GARVIN, Primary Examiner US. Cl. X.R.

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