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Publication numberUS3341542 A
Publication typeGrant
Publication dateSep 12, 1967
Filing dateJul 1, 1965
Priority dateMar 30, 1959
Also published asDE1570871A1, DE1794292B1, US3172892, US3219666, US3278550
Publication numberUS 3341542 A, US 3341542A, US-A-3341542, US3341542 A, US3341542A
InventorsSuer William M Le, George R Norman
Original AssigneeLubrizol Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Oil soluble acrylated nitrogen compounds having a polar acyl, acylimidoyl or acyloxy group with a nitrogen atom attached directly thereto
US 3341542 A
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Description  (OCR text may contain errors)

United States Patent 3,341,542 OIL SOLUBLE ACRYLATED NITROGEN CGM- POUNDS HAVING A POLAR ACYL, ACYL- IMHDOYL 0R ACYLQXY GROUP WITH A NITROGEN ATOM ATTACHED DIRECTLY THERETO William M. Le Suer, Cleveland, and George R. Norman, Lyndhnrst, Ohio, assignors to The Lubrizol Corporation, Wickliife, Ohio, a corporation of Ohio No Drawing. ()riginal application July 21, 1961, Ser. No. 126,809, now Patent No. 3,219,666, dated Nov. 23, 1965. Divided and this application July 1, 1965, Ser. No. 468,948

Claims. (Cl. 260-268) This application is a division of co-pending application Ser. No. 126,80, filed July 21, 1961, now US. 3,219,666 which is a continuation-in-part of application Ser. No. 802,667, filed Mar. 30, 1959, and now US 3,172,892.

This invention relates to oil-soluble nitrogen-containing compositions and to the process of preparing the same. The compositions of this invention are useful as dispersing agents in lubricants, especially lubricants intended for use in the crankcase of internal combustion engines, gears, and power transmitting units.

One of the principal problems associated with presentday crankcase lubricants is that posed by the inevitable presence in the lubricant of foreign particles such as dirt, soot, water and decomposition products resulting from breakdown of the lubricating oil. Even if there were none of this latter contaminant present, the very nature of the design of the modern internal combustion engine is such that a significant amount of foreign matter will accumulate in the crankcase. Perhaps the most important of these contaminants is Water because it seems to be responsible for the deposition of a mayonnaise-like sludge. It appears that if there were no water present the solid components of the mayonnaise-like sludge would circulate with the oil and be removed by the oil filter. It will be readily appreciated that the deposition of the sludge presents a serious problem with respect to the efiicient operation of the engine and that it is desirable to prevent such deposition of sludge-like material.

The presence of water and the precursors of sludge in a lubricating oil is dependent largely upon the operating temperature of the oil. If the oil is operated at a high temperature the water, of course, will be eliminated by evaporation about as fast as it accumulates. In the absence of water, as stated above, the other foreign particles will be removed by the filter. At low oil temperatures, on the other hand, water will accumulate and so consequently will sludge. It is apparent that the environment in which a crankcase lubricant is maintained will determine to a large extent the ultimate performance of that lubricant.

High operating temperatures are characteristic of a lubricant in an engine that is run at relatively constant high speed. Thus, in an engine that is run at 60 miles per hour for a long period of time it is very unlikely that there will be any accumulation of Water and it is similarly unlikely that there will be any formation and deposition of sludge, but in ordinary stop-and-go driving such as is the case with taxicabs, delivery trucks, police cruisers, etc., the crankcase lubricant will be alternately hot and cold, an ideal environment for the accumulation of water. In such cases the formation of sludge is a serious problem. This problem has been with the automotive industry for many years and its solution has been approached by the use of known detergents such as metal phenates and sulfonates but without notable success. Although such known detergents are very effective in solving the detergency problems associated with motor oils at high temperatures they have not been particularly elfective in solving the problems associated with loW temperature operation or, to put it better, those problems which are associated with crankcase lubricants in engines which are operated at alternating high and low temperatures.

It is accordingly a principal object of this invention to provide novel compositions of matter.

It is also an object of this invention to provide compositions which are adapted for use as additives in hydrocarbon oils.

It is also an object of this invention to provide compositions which are effective as detergents in lubricating compositions.

It is another object of this invention to provide a novel process for the preparation of products which are effective as dispersants in lubricant compositions.

It is another object of this invention to provide novel compositions which are effective dispersants in lubricant compositions intended for use in engines operated at alternating high and low temperatures.

It is another object of this invention to provide improved hydrocarbon oil compositions.

It is another object of this invention to provide improved lubricating compositions.

It is another object of this invention to provide improved fuel compositions.

These and other objects are achieved in accordance with this invention by providing a detergent composition comprising an oil-soluble, acylated nitrogen composition characterized by the presence within its structure of (A) a substantially hydrocarbon-substituted polar group selected from the class consisting of acyl, acylimidoyl, and acyloxy radicals wherein the substantially hydrocarbon substituent contains at least about 50 aliphatic carbon atoms and (B) a nitrogen-containing group characterized by a nitrogen atom attached directly to said relatively polar group.

A critical aspect of this invention is the size of the substantially hydrocarbon substituent in the acylated nirogen compounds. Thus, only acylated nitrogen compositions having at least about 50 aliphatic carbon atoms in the substantially hydrocarbon substituent are contemplated as being within the scope of this invention. Fur thermore, in the case of acylated nitrogen compositions having two or more polar groups in a molecule, the substantially hydrocarbon substituent must then contain at least about 25 aliphatic carbon atoms per each polar group. This lower limit is based not only upon the consideration of the oil-solubility of the acylated nitrogen compositions but also upon the effectiveness of such compounds as additives in hydrocarbon oils for the purposes of this invention. It has now been discovered that While acylated nitrogen compositions having less than the minimum number of such aliphatic carbon atoms may be sufiiciently oil-soluble, they nevertheless are not sufficiently effective to be useful as additives of this invention. Furthermore, it has been discovered that their eifectiveness diminishes sharply with a corresponding decrease in the size of the substantially hydrocarbon substituent so that acylated nitrogen compositions having less than about 35 aliphatic carbon atoms in such substituent either are ineffective or produce detrimental results when added to a hydrocarbon oil.

Another important aspect of this invention is the structural constitution of the substantially hydrocarbon substituent. Thus, the radical prefer-ably should be substantially saturated, i.e., at least about of the total number of carbon-to-carbon covalent linkages are saturated linkages. An excessive proportion of unsaturated linkages renders the molecule susceptible to oxidation, degradation, and polymerization and results in products unsuitable for use in hydrocarbon oils in many applications.

The substantially hydrocarbon substituent of the acylated nitrogen compositions of this invention preferably should be substantially free from large oil-solubilizing pendant groups, i.e., groups having more than about 6 aliphatic carbon atoms. While some large oil-solubilizing pendant groups may be present, they preferably should be present in proportions less than about one such group for every 25 aliphatic carbon atoms in the main hydrocarbon chain. A higher proportion of large pendant groups impairs the effectiveness of the acylated nitrogen compositions of this inve tion as additives in hydrocarbon oils.

The substantially hydrocarbon substituent may contain polar substituents provided, however, that the polar substituents are not present in proportions sufi'iciently large to alter significantly the hydrocarbon character of the radical. The polar substituents are exemplified by chloro, bromo, keto, ethereal, aldehydo, and notro, etc. The upper limit with respect to the proportion of such polar substituents in the radical is approximately 10% based on the weight of the hydrocarbon portion of the radical.

The sources of the substantially hydrocarbon substituent include principally the high molecular weight substantially saturated petroleum fractions and substantially saturated olefin polymers, particularly polymers of monoolefins having from 2 to about 30 carbon atoms. The especially useful polymers are the polymers of l-monoolefins such as ethylene, propene, l-butene, isobutene, l-hexene, l-octene, 2-methyl-1-heptene, 3-cyclohexyl-lbutene, and 2-methyl-5-propyl-l-hexene. Polymers of medial olefins, i.e., olefins in which the olefinic linkage is not at the terminal position, likewise are useful. They are illustrated by Z-butene, 3-pentene, and 4-octene.

Also useful are the interpolymers of the olefins such as those illustrated above with other interpolymerizable olefinic substances such as aromatic olefins, cyclic olefins, and polyolefins. Such interpolymers include, for example, those prepared by polymerizing isobutene with styrene; isobutene with butadiene; propene with isoprene; ethylene with piperylene; isobutene with chloroprene; isobutene with p-methyl styrene; l-hexene with 1,3-hexadiene; l-octene with l-hexene; l-heptene with l-pentene; 3- methyl-i-butene with l-octene; 3,3-dimethyl-l-pentene with l-hexene; isobutene with styrene and piperylene; etc.

The relative proportions of the mono-olefins to the other monomers in the interpolymers influence the stability and oil-solubility of the final acylated nitrogen compositions derived from such interpolymers. Thus, for reasons of oil-solubility and stability the interpolymers contemplated for use in this invention should be substantially aliphatic and substantially saturated, i.e., they should contain at least about 80%, preferably at least about 95%, on a weight basis of units derived from the aliphatic monoolefins and no more than about 5% of olefinic linkages based on the total number of carbon-to-carbo'n covalent linkages. In most instances, the percentage of olefinic linkages should be less than about 2% of the total number of carbon-to-carbon covalent linkages.

Specific examples of such interpolymers include copolymer of 95% (by weight) of isobutene with 5% of styrene; terpolymer of 98% of isobutene with 1% of piperylene and 1% of chloroprene; terpolymer of 95% of isobutene with 2% of l-butene and 3% of l-hexene; terpolymer of 60% of isobutene with 20% of l-pentene and 20% of l-octene; copolymer of 80% of l-hexene and 20% of l-heptene; terpolymer of 90% of isobutene with 2% of cyclohexene and 8% of propene; and copolymer of 80% of ethylene and 20% of propene.

Another source of the substantially hydrocarbon radical comprises saturated aliphatic hydrocarbons such as highly refined high molecular weight white oils or synthetic alkanes such as are obtained by hydrogenation of high molecular Weight olefin polymers illustrated above or high molecular weight olefinic substances.

The use of olefin polymers having molecular weight of about 750-5000 is preferred. Higher molecular weight olefin polymers having molecular weights from about 10,000 to about 100,000 or higher have been found to impart also viscosity index improving properties to the acylated nitrogen compositions of this invention. In many instances the use of such higher molecular weight olefin polymers is desirable. On the other hand, olefin polymers having molecular weights less than about 700 are not useful.

The relatively polar group of the acylated nitrogen compositions is selected from the class consisting of acyl, acylirnidoyl, and acyloxy radicals. These radicals have the following structural configurations, respectively:

wherein R represents the substantially hydrocarbon substituent described hereinbefore and R represents a hydrogen radical or an organic radical such as a hydrocarbon radical or a polar-substituted hydrocarbon radical.

The nitrogen-containing group of the acylated nitrogen compositions of this invention is derived from compounds characterized by a radical having the structural configuration l The two remaining valences of the nitrogen atom of the above radical preferably are satisfied by hydrogen, amino, or organic radicals bonded to said nitrogen atom through direct carbon-to-nitrogen linkages. Thus, the compounds from which the nitrogen-containing group may be derived include principally ammonia, aliphatic amines, aromatic amines, heterocyclic amines or carbocyclic amines. The amines may be primary or secondary amines and may also be polyamines such as alkylene amines, arylene amines, cyclic polyamines, and the hydroxy-substituted derivatives of such polyamines.

Specific amines of these types are methylamine, N methyl-ethylamine, N methyl octylamine, N cyclohexyl-aniline, dibutylamine, cyclohexylamine, aniline,

di(p-methylphenyl)amine, dodecylamine, octadecylamine,

o-phenylenediamine, N,N'-di-n-butyl-p phenylene diamine, morpholine, piperazine, tetrahydropyrazine, indole, hexahydro-1,3,5-triazine, 1-H 1,2,4 -triazole, melamine, bis(p aminophe'nyDmethane, phenyl methylenimine, menthanediamine, cyclohexamine, pyrrolidine, 3-amino- 5,6-diphenyl-1,2,4-triazine, quinonediimine, 1,3-indandiimine, 2-octadecyl-imidazoline, 2-phenyl-4-methyl imidazolidine, oxazolidine, ethanolamine, diethanolamine, and Z-heptyl-oxazolidine.

A preferred source of the nitrogen-containing group consists of polyamines, especially alkylene amines conforming for the most part to the formula wherein n is an integer preferably less than about 10, A is a substantially hydrocarbon or hydrogen radical, and the alkylene radical is preferably a lower alkylene radical having less than about 8 carbon atoms. The alkylene amines include principally methylene amines, ethylene amines, butylene amines, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines, and also the cyclic and the higher homologs of amines such as piperazines and amino-alkyl-substituted piperazines. They are exemplified specifically by: ethylene diamine, triethylene tetramine, propylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene)triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene) triamine, 2-heptyl-3-(Z-aminopropyl)imidazoline, 4-rnethylimidazoline, 1,3-bis(2-aminoethyl)imidazoline, pyrimidine, l-(2 aminopropyl)piperazine, l,4-bis(2 aminoethyl)piperazine, and Z-methyl-l-(Z- aminobutyDpiperazine. Higher homologs such as are obtained by condensing two or more of the above-illustrated alkylene amines likewise are useful.

The ethylene amines are especially useful. They are described in some detail under the heading Ethylene Amines in Encyclopedia of Chemical Technology, Kirk and Othmer, vol. 5, pp. 898-905, Interscience Publishers, New York (1950). Such compounds are prepared most conveniently by the reaction of an alkylene chloride with ammonia. The reaction results in the production of somewhat complex mixtures of alkylene amines, including cyclic condensation products such as piperazines. These mixtures find use in the process of this invention. On the other hand, quite satisfactory products may be obtained also by the use of pure alkylene amines. An especially useful alkylene amine for reasons of economy as well as effectiveness of the products derived therefrom is a mixture of ethylene amines prepared by the reaction of ethylene chloride and ammonia and having a composition which corresponds to that of tetraethylene pentamine.

Hydroxyalkyl-substituted alkylene amines, i.e., alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atoms, likewise are contemplated for use herein. The hydroxyalkyhsubstituted alkylene amines are preferably those in which the alkyl group is a lower alkyl group, i.e., having less than about 6 carbon atoms. Examples of such amines include N-(Z-hydroxyethyl)-ethylene diamine, N,N'-bis(2-hydroxyethyl)ethylene diamine, 1-(Z-hydroxyethyl)piperazine, mono-hydroXypropyl-substituted diethylene triamine, 1,4-bis(2-hydroxypropyl) piperazine, di hydroxypropyl-substituted tetraethylene pentamine, N-(3 hydroxypropyl)tetramethylene diamine, and 2-heptadecyl-1-(2-hydroxyethyl)imidazoline.

Higher homologs such as are obtained by condensation of the above-illustrated alkylene amines or hydroxy alkylsubstituted alkylene amines through amino radicals or through hydroxy radicals are likewise useful. It will be appreciated that condensation through amino radicals results in a higher amine accompanied with removal of ammonia and that condensation through the hydroxy radicals results in products containing ether linkages accompanied with removal of water.

Other sources of the nitrogen-containing grou include ureas, thioureas, hydrazines, guanidines, amidines, amides, thioamides, cyanamides, etc. Specific examples illustrating such compounds are: hydrazine, phenylhydrazine, N,N'- diphenylhydrazine, octadecylhydrazine, benzoylhydrazine, urea, thiourea, N-butylurea, stearylamide, oleylamide, guanidine, 1,3-diphenylguanidine, 1,2,3-tri'butylguanidine, benzamidine, octadecamidine, N,N'-dimethylstearamidine, cyanamide, dicyanidiamide, guanylurea, aminoguanidine, etc.

As indicated previously, the nitrogen-containing group in the acylated nitrogen compositions of this invention is characterized by a nitrogen atom attached directly to the relatively polar group. It will be appreciated, of course, that the linkage between a nitrogen atom and an acyl radical is representative of an amide or an imide structure, that the linkage between a nitrogen atom and an acylimidoyl radical is representative of an amidine structure, and that the linkage between a nitrogen atom and an acyloxy radical is representative of an ammoniumcarboxylic acid salt structure. Thus, the acylated nitrogen compositions of this invention are characterized by amide, imide, amidine, or salt linkages and in many instances a mixture of such linkages. Those containing two such linkages separated by a lower alkylene radical (i.e., one having less than about 6 carbon atoms), such as are derived from succinic, glutaric, or adipic radicals, are especially preferred in this invention.

A convenient method for preparing the acylated nitrogen compositions of this invention comprises reacting a high molecular weight acid-producing compound characterized by the presence within its structure of a high molecular weight oil-solubilizing group having at least about 50 aliphatic carbon atoms and at least one acidproducing group having the structural configuration.

wherein X is selected from the class consisting of halogen, hydroxy, hydrocarbon-oxy, and acyloxy radicals, with at least about one-half an equivalent amount of a nitrogen containing compound characterized by the presence within its structure of at least one radical having the structural configuration The above process involves a reaction between the acidproducing group with the nitrogen-containing radical to result in the direct attachment of the nitrogen atoms to a polar radical, i.e., acyl, acylimidoyl, or acyloxy radical derived from the acid-producing group. The linkage formed between the nitrogen atom and the polar radical may thus be that representative of a salt, amide, imide, or amidine radical. In most instances the product of the above process contains a mixture of linkages representative of such radicals. The precise relative proportions of such radicals in the product usually are not known as they depend to a large measure upon the type of the acidproclucing group and the nitrogen-containing radical involved in the reaction and also upon the environment (e.g., temperature) in which the reaction is carried out. To illustrate, the reaction involving an acid or anhydride group with an amino nitrogen-containing radical at relatively low temperatures such as below about 60 C. results predominantly in a salt linkage i.e.,

but at relatively high temperatures such as above about C. results predominantly in an amide, imide, or amidine linkage i.e.,

am a e In any event, however, the products obtained by the above process, irrespective of the nature or relative proportions of the linkages present therein, have been found to be effective as additives in hydrocarbon oils for the purposes of this invention.

The acid-producing compounds contemplated for use in the above process include mono-carboxylic and poly-carboxylic acids, acid halides, esters, and anhydrides, and also mixtures of such compounds. The nature of the oilsolubilizing group in such compounds should be the same as that which characterized the substantially hydrocarbon substituent, described previously, in the acylated nitrogen compositions of this invention.

The substantially saturated, aliphatic hydrocarbon-substituted succinic acids and anhydrides are especially preferred for use as the acid-producing reactant in this process for reasons of the particular effectiveness of the products obtained from such compounds as additives in hydrocarbon oils. The succinic compounds are readily available from the reaction of maleic anhydride with a high molecular weight olefin or a chlorinated hydrocarbon such as the olefin polymer described hereinabove. The reaction involves merely heating the two reactants at a temperature about 100-200 C. The product from such a reaction is an alkenyl succinic anhydride. The alkenyl group may be hydrogenated to an alkyl group. The anhydride may be hydrolyzed by treatment with water or steam to the corresponding acid. Either the anhydride or the acid may be converted to the corresponding acid halide or ester by reaction with, e.g., phosphorus halide, phenols, or alcohols.

In lieu of the high molecular weight olefins or chlorinated hydrocarbons, other high molecular weight hydrocarbons containing an activating polar substituent, i.e., a substituent which is capable of activating the hydrocarbon molecule in respect to reaction with maleic acid or anhydride may be used in the above-illustrated reaction for preparing the succinic compounds. Such polar substituents may be illustrated by sulfide, disulfide, nitro, mercaptan, bromine, ketone, and aldehyde radicals. Examples of such polar-substituted hydrocarbons include polypropene sulfide, di-polyisobutene disulfide, nitrated mineral oil, dipolyethylene sulfide, brominated polyethylene, etc. Another method useful for preparing the succinic acids and anhydrides involves the reaction of itaconic acid with a high molecular weight olefin or a polar-substituted hydrocarbon at a temperature usually within the range from about 100 C. to about 200 C.

The polycarboxylic acids and derivatives thereof having more than two carboxylic radicals per molecule which are contemplated for use in this invention are those containing at least about 50 aliphatic carbon atoms per molecule and furthermore at least about 25 aliphatic carbon atoms per each carboxylic radical. Such acids may be prepared by halogenating a high molecular Weight hydrocarbon such as the olefin polymer described hereinabove to produce a poly-halogenated product, converting the poly-halogenated product to a poly-nitrile, and then hydrolyzing the poly-nitrile. They may be prepared also by oxidation of a high molecular weight polyhydric alcohol with potassium permanganate, nitric acid, or a like oxidizing agent. Another method for preparing such polycarboxylic acids involves the reaction of an olefin or a polar-substituted hydrocarbon such as a chloro-polyisobutene with an unsaturated poly-carboxylic acid such as Z-pentene-1,3,5-tricarboxylic acid obtained by dehydration of citric acid.

The mono carboxylic acids and derivatives thereof may be obtained by oxidizing a mono-hydric alcohol with potassium permanganate or by reacting a halogenated high molecular olefin polymer with a ketone. Another convenient method for preparing the mono-carboxylic acids involves the reaction of metallic sodium with an acetoacetic ester or a malonic ester of an alkanol to form a sodium derivative of the ester and the subsequent reaction of the sodium derivative with a halogenated high molecular weight hydrocarbon such as brominated wax or brominated polyisobutene.

The mono-carboxylic and poly-carboxylic acid anhydrides are obtained by dehydrating the corresponding acids. Dehydration is readily accomplished by heating the acid to a temperature above about 70 C. preferably in the presence of a dehydration agent, e.g., acetic anhydride. Cyclic anhydrides are usually obtained from polycarboxylic acids having the acid radicals separated by no more than three carbon atoms such as substituted succinic or glutaric acids, whereas linear polymeric anhydrides are obtained from poly-carboxylic acids having the acid radicals separated by four or more carbon atoms.

The acid halides of the mono-carboxylic and polycarboxylic acids can be prepared by the reaction of the acids or their anhydrides with a halogenation agent such as phosphorus tribromide, phosphorus pentachloride, or thionyl chloride. The esters of such acids can be prepared simply by the reaction of the acids or their anhydrides with an alcohol or a phenolic compound such as methanol, ethanol, octadecanol, cyclohexanol, phenol, naphthol, octylphenol, etc. The esterification is usually promoted by the use of an alkaline catalyst such as sodium hydroxide or sodium alkoxide or an acidic catalyst such as sulfuric acid. The nature of the alcoholic or phenolic portion of the ester radical appears to have little influence on the utility of such ester as reactant in the process described hereinabove.

The nitrogen-containing reactants useful in the above process are the compounds, described previously in this specification, from which the nitrogen-containing group the acy-lated nitrogen compositions of this invention can be derived.

The above process is usually carried out by heating a mixture of the acidproducing compound and the nitrogen-containing reactant at a temperature above about 0., preferably within the range from about C. to about 250 C. Howeven when an acid or anhydride is employed in reactions with an amino nitrogencontaining reactant, the process may be carried out at a lower temperature such as room temperature to obtain products having predominantly salt linkages or mixed salt-amide linkages. Such products may be converted, if desired, by heating to about 80 C. to products having predominantly amide, imide, or amidine linkages. The use of a solvent such as benzene, toluene, naphtha, mineral oil, xylene, n-hexane, or the like is often desirable in the above process to facilitate the control of the reaction temperature.

The relative proportions of the acid-producing compounds and the nitrogen-containing reactants to be used in the above process are such that at least about onehalf of a stoichiometrically equivalent amount of the nitrogen-containing reactant is used for each equivalent of the acid-producing compound used. In this regard it will be noted that the equivalent Weight of the nitrogen-containing reactant is based upon the number of the nitrogencontaining radicals defined by the structural configuration -NH. Similarly the equivalent weight of the acidproducing compound is based upon the number of the acid-producing radicals defined by the structural configuration Thus, ethylene diamine has two equivalents per mole; amino guanidine has four equivalents per mole; a succinic acid or ester has two equivalents per mole, etc. The upper limit of the useful amount of the nitrogencontaining reactant appears to be about two moles for each equivalent of the acid-producing compound used. Such amount is required, for instance, in the formation of products having predominantly amidine linkages. Beyond this limit, the excess amount of the nitrogen-containing reactant appears not to take part in the reaction and thus simply remains in the product apparently without any adverse effects. On the other hand, the lower limit of about one-half equivalent of the nitrogen-containing reactant used for each equivalent of the acid-producing compound is based upon the stoichiometry for the formation of products having predominantly imide linkages. In most instances, the preferred amount of the nitrogencontainiug reactant is approximately one equivalent for each equivalent of the acid-producing compound used.

The following examples illustrate the processes useful for preparing the acylated nitrogen compounds of this invention:

EXAMPLE 1 A polyisobutenyl succinic anhydride is prepared by the reaction of a chlorinated polyisobutylene with maleic anhydride at 200 C. The polyisobutenyl radical has an average molecular weight of. 850 and the resulting alkenyl succinic anhydride is found to have an acid number of 113 (corresponding to an equivalent weight of 500). To

a mixture of 500 grams (1 equivalent) of this polyisobutenyl succinic anhydride and 160 grams of toluene there is added at room temperature 35 grams (1 equivalent) of diethylene triamine. The addition is made portionwise throughout a period of minutes, and an initial exothermic reaction caused the temperature to rise to 50 C. The mixture then is heated and a water-toluene azeotrope distilled from the mixture. When no more water would distill the mixture is heated to 15 C. at reduced pressure to remove the toluene. The re 'due is diluted with 350 grams of mineral oil and this solution is found to have a nitrogen content of 1.6%.

EXAMPLE 2 The procedure of Example 1 is repeated using 55.5 grams (1.5 equivalents) of an ethylene amine mixture having a composition corresponding to that of triethylene tetramine. The resulting product has a nitrogen content EXAMPLE 4 The procedure of Example 1 is repeated using 55.0 grams 1.5 equivalents) of triethylene tetramine as the amine reactant. The resulting product has a nitrogen content of 2.9%.

EXAMPLE 5 To a mixture of 140 grams of toluene and 400 grams (0.78 equivalent) of a polyisobutenyl succinic anhydride (having an acid number of 109 and prepared from maleic anhydride and the chlorinated polyisobutylene of Example 1) there is added at room temperature 63.6 grams (1.55 equivalents) of an ethylene amine mixture having an average composition corresponding to that of tetraethylene pentamine and available from Carbide and Carbon under the trade name Polyamine H. The mixture is heated to distill the Water-toluene azeotrope and then to 150 C. at reduced pressure to remove the remaining toluene. The residual polyamide has a nitrogen content of EXAMPLE 6 The procedure of Example 1 is repeated using 46 grams 1.5 equivalents) of ethylene diamine as the amine reactant. The product which resulted has a nitrogen content of 1.5%.

EXAMPLE 7 A polyisobutenyl succinic anhydride having an acid number of 105 and an equivalent weight of 540 is prepared by the reaction of a chlorinated polyisobutylene (having an average molecular Weight of 1,050 and a chlorine content of 4.3%) and maleic anhydride. To a weight of the polyisobutenyl succinic anhydride and 160 parts by weight of mineral oil there is added at 6595 C. an equivalent amount parts by weight) of Polyamine H (identified in Example 5). This mixture then is heated to 150 C. to distill all of the water formed in the reaction. Nitrogen is bubbled through the mixture at this temperature to insure removal of the last traces of water. The residue is diluted by 79 parts by weight of mineral oil and this oil solution found to have a nitrogen content of 1.6%.

EXAMPLE 8 A mixture of 2,112 grams (3.9 equivalents) of the polyisobutenyl succinic anhydride of Example 7, 136 grams (3.9 equivalents) of diethylene triamine, and 1,060 grams of mineral oil is heated at 140150 C. for one hour. Nitrogen is bubbled through the temperature for four more hours to aid in the removal of Water. The residue is diluted with 420' grams of mineral oil and this oil solution is found to have a nitrogen content of 1.3%.

EXAMPLE 9 EXAMPLE 10 A polypropenyl succinic anhydride is prepared by the reaction of a chlorinated polypropylene (having a molecular weight of about 900 and a chlorine content of 4%) and maleic anhydride at 200 C. The product has an acid number of 75. To a mixture of 390 grams (0.52 equivalent) of this polypropenyl succinic anhydride, 500 grams of toluene, and 170 grams of mineral oil there is added portionwise 22 grams (0.52 equivalent) of Polyamine H. The reaction mixture is heated at reflux temperature for three hours and water removed from an azeotrope with toluene. The toluene then is removed by heating to C./20 millimeters. The residue was found to contain 1.3% of nitrogen.

EXAMPLE 11 A substituted succinic anhydride is prepared by reacting maleic anhydride with a chlorinated copolymer of isobutylene and styrene. The copolymer consists of 94 parts by weight of isobutylene units and 6 parts by weight of styrene units, has an average molecular weight of 1,200, and is chlorinated to a chlorine content of 2.8% by weight. The resulting substituted succinic anhydride has an acid number of 40. To 710 grams (0.51 equivalent) of this substituted succinic anhydride and 500 grams of toluene there is added portionwise 22 grams (0.51 equivalent) of Polyamine H. The mixture is heated at reflux temperature for three hours to remove by azeotropic distillation all of the water formed in the reaction, and then at 150 C./20 millimeters to remove the toluene. The residue contains 1.1% by Weight of nitrogen.

EXAMPLE 12 A substituted succinic anhydride is prepared by reacting maleic anhydride with a chlorinated copolymer of isobutylene and isoprene. The copolymer consists of 99 parts by weight of isobutylene units and 1% by weight of isoprene units. The molecular weight of the copolymer is 28,000 and the chlorine content of the chlorinated co polymer is 1.95%. The resulting alkenyl succinic anhydride has an acid number of 54. To a mixture of 228 toluene is distilled by heating to 150 C./20 millimeters. The residue is found to have a nitrogen content of 1.1%.

EXAMPLE 13 A polyisobutenyl succinic anhydride is prepared by the reaction of a chorinated polyisobutylene with maleic anhydride. The chlorinated polyisobutylene has a chlorine content of 2% and an average moleculer weight of 1 1 heating to 150 C./20 millimeters. The nitrogen content of the residue is 1.3%.

EXAMPLE 14 The procedure of Example is repeated except that 0.94 equivalent of Polyamine H is used instead of 1.55 equivalents. The nitrogen content of the product is 3%.

EXAMPLE 15 A polyisobutenyl-substituted succinic acid is prepared by hydrolysis of the corresponding anhydride (prepared in turn by the condensation of a chlorinated polyisobutylene and maleic anhydride). To 1152 grams (1.5 equivalents) of a 70% mineral oil solution of this polyisobutenyl succinic acid having an acid number of 62 there is added at room temperature 59.5 grams (1.5 equivalents) of Polyamine H. This mixture is heated at 150- 167 C. for 7 hours during which time a total of 19.5 grams of water is distilled from the mixture. Theresidue is diluted with 174 grams of mineral oil and then filtered at 150 C. The filtrate has a nitrogen content of 1.6%.

EXAMPLE 16 A mixture of 1,056 grams (2.0 equivalents) of the polyisobutenyl succinic anhydride of the preceding example (in which the polyisobutenyl group has a molecular weight of 850), 89 grams (2.0 equivalents) of di- (1,2-propylene) triamine (having a nitrogen content of 31.3%), 370 grams of mineral oil and 100 grams of toluene is heated at reflux temperature (180190 C.) for 5 hours. A total of 18 grams of water is collected from the water-toluene azetrope. The residue is heated to 150 C./ mm. to remove any last traces of water which might have remained. The nitrogen analysis of this residue is 1.9%.

EXAMPLE 17 A polyisobutylene having an average molecular weight of 50,000 is chlorinated to a chlorine content of 10% by weight. This chlorinated polyisobutylene is reacted with maleic anhydride to produce the corresponding polyisobutenyl succinic anhydride having an acid number of 24. To 6,000 grams (2.55 equivalents) of this anhydride there is added portionwise at 70-105 C. 108 grams (2.55 equivalents) of Polyamine H over a period of 45 minutes. The resulting mixture is heated for four hours at 160- 180 C. while nitrogen is bubbled throughout to remove water. When all of the water has been removed the product is filtered and the filtrate found to have a nitrogen content of 0.6%.

EXAMPLE 18 A mixture of 1 equivalent of a pol. isobutene-substituted succinic anhydride having an ac d number of 98 (prepared according to the procedure described in Example 1) and 1 equivalent of an acrolein-ammonia (molar ratio of 1:1) interpolymer having a nitrogen content of 23% by weight is diluted with 40% by its Weight of a mineral oil. The resulting mixture is heated to 155 C. and nitrogen is bubbled through the mixture at this temperature for 5 hours. The residue is found to have a nitrogen content of 1.35%.

EXAMPLE 19 A cyanoethyl-substituted ethylene amine is prepared by mixing 212 grams of acrylonitrile with 216 grams of an ethylene amine mixture consisting of 75% by weight of triethylene tetramine and by weight of diethylene triamine at room temperature and heating the mixture at 110130 C. for 5 hours and then to 125 C./ mm. To a mixture of 1110 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 825 grams of mineral oil there is added at 60 C. 143 grams dropwise of the above cyanoethyl-substituted ethylene amine (having a nitrogen content of 31.8%). The mixture is heated at 150l60 C. for 5 hours while being purged with piperazine and 356 12 of 6 cc. of water is removed by distillahas a nitrogen content of 1.66%.

EXAMPLE 20 To a mixture of 430 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 355 grams of mineral oil there is added at 60-80 C. 108 grams of N-aminopropyl morpholine throughout a period of 1 hour. The mixture is heated at 150-155 C. for 5 hours until no more water distills. The residue is found to have a nitrogen content of 2.3%.

EXAMPLE 21 To a mixture of 430 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 304 grams of mineral oil there is added at 60-80 C. 33 grams of dipropylene triamine. The mixture is then heated at 150-155 C. for 5 hours until no more water distills. The residue is found to have a nitrogen content of 1.45%.

EXAMPLE 22 EXAMPLE 23 A mixture of 286 grams of polyisobutene-substituted succinic anhydride of Example 1, 96 grams of N,N-di butyl ethylenediamine and 252 grams of mineral oil is prepared at 60 C. and heated at 150-165 C. for 5 hours While being purged with nitrogen. The residue is found to have a nitrogen content of 2.24%.

EXAMPLE 24 A mixture of 417 grams of polyisobutene-substituted succinic anhydride of Example 1, 30 grams of N-(Z- aminoethyl)trimethylene diamine and 293 grams of mineral oil is prepared at 60-80 C. and then heated at 150-155 C. for 5 hours while being purged with nitrogen. The residue is found to have a nitrogen content of 1.51%.

nitrogen. A total tion. The residue EXAMPLE 25 A mixture of 430 grams of the polyisobutene-substituted succinic anhydride of Example 1, 64 grams of 1,1- (dimeth-ylaminoethyl) 4 methyl-piperazine and 324 grams of mineral oil is prepared at 60 C. and then heated at 150-155 C. while being blown with nitrogen. The residue is found to have a nitrogen content of 1.81%.

EXAMPLE 26 A mixture of 416 grams of polyisobutene-substituted succinic anhydride of Example 1, 124 grams of N-phenyl grams of mineral oil is prepared at 60 C. and then heated at 150-155 C. for 5 hours while being purged with nitrogen. No water is removed by such heating. The residue is found to have a nitrogen content of 2.07%.

EXAMPLE 27 A mixture of 1,110 grams of polyisobutene-substituted succinic anhydride of Example 1, grams of anthranilic acid and 844 grams of mineral oil is heated at 100 C. for 2 hours. The mixture is cooled and is mixed with 72 grams of a mixture consisting of 75% by weight of triethylene tetramine and 25 by weight of diethylenetriamine at 60-80 C. The resulting mixture is heated at 155 C. for 5 hours while being purged with nitrogen. The residue is found to have a nitrogen content of 1.72%.

A diisobutenyl-substituted ethylene amine is prepared by reacting 590 grams of diisobutenyl chloride and 264 grams of a mixture consisting of 75% by weight of triethylene tetramine and by weight of diethylene triamine in the presence of 264 grams of potassium hydroxide (85% purity) and 2,200 grams of isopropyl alcohol at 85 90 C. A mixture of 528 grams of polyisobutenesubstituted succinic anhydride of Example 1, 101 grams of the above diisobutenyl-substituted ethylene amine and 411 grams of mineral oil is heated at 150-160 C. while being purged with nitrogen until no more water distills. The residue has a nitrogen content of 1.98%.

EXAMPLE 29 A mixture of 45 grams of di-(polypropoxy)cocoamine having a molecular weight of 2265, 22 grams of polyisobutene-substituted succinic anhydride of Example 1 and and 44 grams of mineral oil is heated at 150-155 C. for 7 hours. The residue is found to have a nitrogen content of 0.25%.

EXAMPLE 30 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 159 grams of menthane diamine and 500 grams of mineral oil is prepared at 70-100 C. and heated at 150190 C. while being blown with nitrogen until no Water distills. The residue is diluted with 258 grams of mineral oil and the solution is found to have a nitrogen content of 1.32%.

EXAMPLE 31 EXAMPLE 32 A mixture of 206 grams of N,N'-disecondary-'butyl pphenylene diamine, 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 500 grams of mineral oil is prepared at 85 C. and heated at 150- 200 C. for 9.5 hours. The mixture is diluted with 290 grams of mineral oil, heated to 160 C. and filtered. The filtrate is found to have a nitrogen content of 1.29%.

EXAMPLE 33 To 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 500 grams of mineral oil there is added 17.6 grams of hydrazine at 70 80 C. The reaction is exothermic. The mixture is heated at 140150 C. for 1 hour whereupon 9 grams of water is collected as the distillate. To the residue there is then added 40 grams of an ethylene amine mixture having an average composition corresponding to that of tetraethylene pentarnine at 70-80 C. The mixture is then heated at 150-160 C. while being purged with nitrogen until no more water is removed by distillation. The residue is diluted with 200 grams of mineral oil, heated to 160 C. and filtered. The filtrate has a nitrogen content of 1.16%.

EXAMPLE 34 To a solution of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1 in 500 grams of mineral oil there is added 28 grams of 1,1-dimethyl hydrazine at -60 C. The mixture is heated at 95 C. for 3 hours and then mixed with 40 grams of an ethylene amine mixture having an average composition corresponding to that of tetraethylene pentamine at 85 95 C. The mixture is then heated at 150-185 C. for 6 1 4 grams of water is collected as the distillate. The residue is diluted with 197 grams of mineral oil, heated to 160 C. and filtered. The filtrate has a nitrogen content of 1.53%.

EXAMPLE 35 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 333 grams of 1,2- di(3-aminopropoxy)ethane and 500 grams of mineral oil is heated at 140-170 C. for 5 hours whereupon 18 grams of water is collected as the distillate. The residue is diluted with 380 grams of mineral oil, heated to 160 C. and filtered. The filtrate has a nitrogen content of 2.3%

EXAMPLE 36 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 418 grams of di (3-aminopropoxy ethyl)ether and 500 grams of mineral oil is heated at l50-170 C. for 4 hours. A total of 17 grams of water is collected as the distillate. The residue is diluted with 433 grams of mineral oil, heated to 160 C., and filtered. The filtrate has the nitrogen content of 2.18%.

hours whereupon 14 EXAMPLE 37 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 361 grams of a technical tertiary-alkyl primary amine wherein the tertiary-alkyl radical contains 12-14 carbon atoms and 500 grams of mineral oil is heated at 155250 C. for 13 hours while being purged with nitrogen. The residue is then heated to 150 C./1 mm., diluted with 337 grams of mineral oil, heated to 160 C. and filtered. The filtrate has a nitrogen content of 0.87%.

EXAMPLE 3 8 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 254 grams of aminoguanidine bicarbonate and 500 grams of mineral oil is prepared at C. and heated at 165 C. for 5 hours. The residue is mixed with 223 grams of mineral oil, heated to 150 C., and filtered. The filtrate has the nitrogen content of 3.38%.

EXAMPLE 39 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 103 grams of 2,6- diamino-pyridine and 500 grams of mineral oil is heated at -180 C. for 11 hours while being purged with nitrogen. A total of 16 grams of water is collected as the distillate. The residue is diluted with 223 grams of mineral oil, heated to C. and filtered. The filtrate has a nitrogen content of 2.15%.

EXAMPLE 41 A mixture of 1000 grams of polyisobutene-substituted succinic anhydride of Example 1, 159 grams of cyanoguanidine and 233 grams of toluene is heated at the reflux temperature for 14 hours while 7.15 grams of water is removed by azeotropic distillation. The mixture is diluted with 740 grams of mineral oil and toluene is then removed by heating the mixture to 150 C. The residue is filtered and the filtrate has the nitrogen content of 4.74%.

EXAMPLE 42 A mixture of 1632 grams of polyisobutene-substituted succinic anhydride of Example 1, 207 grams of a conden sation product of acrolein with ammonia (molar ratio of 1:1) having a nitrogen content of 20%, 604 grams of mineral oil and 1750 grams of toluene is heated at the reflux temperature for 3 hours. A total of 31 grams of water is removed as the distillate. Toluene is then removed by heating the mixture to 150 C./ 20 mm. The residue is found to have a nitrogen content of 1.89%.

EXAMPLE 43 A nitrogen-containing compound is prepared by mixing 100 grams of cyanoguanidine with 500 grams of ethylene amine mixture having an average composition corresponding to that of tetraethylene pentamine and heating the mixture at 7080 C. for 3 hours to obtain a homogeneous mass and filtering the mass. A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 96 grams of the above filtrate and 164 grams of toluene is heated at the reflux temperature for hours. The toluene is then removed by heating the mixture to 150 C./ 20 mm. The residue is diluted with 400 grams of mineral oil and filtered. The filtrate has a nitrogen content of 3.43%.

EXAMPLE 44 To a mixture of 544 grams of the polyisobutene-substituted succinic anhydride of Example 1, 283 grams of mineral oil and 281 grams of toluene there is added 30 grams of urea at 45 C. The resulting mixture is heated at 130- 135 C. for 11 hours whereupon 2.5 cc. of water is re moved as the distillate. The residue is then heated to 140 C./20 mm. and filtered. The filtrate has a nitrogen content of 1%.

EXAMPLE 45 A mixture of 1088 grams of the polyisobutene-substituted succinic anhydride of Example 1, 106 grams of dipropylene triamine, 500 grams of toluene is heated at the reflux temperature for 4 hours until no more water distills. The residue is then heated to 150 C./ 20 mm. and diluted with 392 grams of mineral oil. The oil solution is found to have a nitrogen content of 1.74%.

EXAMPLE 46 A mixture of 1000 grams of the polyiso'butene-substituted succinic anhydride of Example 1, 174 grams of phenylbiguanide and 270 grams of toluene is heated at the reflux temperature for 6.5 hours whereupon 25 grams of water is removed by distillation. The residue is diluted with 500 grams of mineral oil and heated to 160 C./20 mm. to distill off toluene. The residue is diluted further with 265 grams of mineral oil, heated to 150 C. and filtered. The filtrate has a nitrogen content of 3.4%.

EXAMPLE 47 A mixture of 920 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 249 grams of bis-(dimethylaminopropyl)amine is heated at reflux temperature until no more Water distills. The residue has a nitrogen content of 4%.

EXAMPLE 48 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 363 grams of aminopropyl octadecylamine and 1314 grams of mineral oil is heated at 200 C. for 24 hours. The residue is filtered. The filtrate has a nitrogen content of 1.02%.

EXAMPLE 49 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 258 grams of di-n-butylamine is heated at 185 C. for 12 hours and then to 200 C./ 25 mm. The residue is diluted with 1157 grams of mineral oil and filtered. The filtrate has a nitrogen content of 0.8%.

EXAMPLE 50 A mixture of 297 grams of the polyisobutene-substituted succinic anhydride of Example 1, 25 grams of mel- 16 amine and 200 grams of mineral oil is heated at 260 C. for 9 hours and then at 290-295 C. for 7 more hours. The residue is mixed with 50 grams of water,

heated at reflux for 7 hours, dried and filtered. The filtrate has a nitrogen content of 2%.

EXAMPLE 51 EXAMPLE 52 A mixture of 1.0 equivalent of a mono-carboxylic acid (prepared by chlorinating a polyisobutene having a molecular weight of 750 to a product having a chlorine content of 3.6% by weight, converting the product to the corresponding nitrile by reaction with an equivalent amount of potassium cyanide in the presence of a catalytic amount of cuprous cyanide and hydrolyzing the resulting nitrile by treatment with 50% excess of a dilute aqueous sulfuric acid at the reflux temperature) and 0.5 equivalent of ethylene diamine is mixed with twice its volume of xylene. The resulting mixture is heated at the reflux temperature until no more water is removed by distillation. The mixture is heated further and the xylene is removed by distillation under reduced pressure. The residue is the acylated nitrogen compound.

EXAMPLE 53 A methyl ester of a high molecular weight monocarboxylic acid is prepared by heating an equi-molar mixture of a chlorinated polyisobutene having a molecular weight of 1000 and a chlorine content of 4.7% by weight and methyl methacrylate at l40220 C. The resulting ester is then heated with a stoichiometrically equivalent amount of triethylene tetramine at l00-200 C. to produce an acylated nitrogen compound of this invention.

EXAMPLE 54 A dimethyl wax-substituted malonate is prepared by reacting dimethyl malonate with sodium ethoxide to form a sodium derivative of the ester, heating the sodium derivative with a brominated wax having 75 carbon atoms and 1 bromine atom per molecule. A mixture of 1.0 equivalent of the ester of 1.0 equivalent of N,N-dibutyl thiourea is dissolved in five times its volume of xylene. The resulting mixture is heated at the reflux temperature until no more water is removed by azeotropic distillation. The mixture is heated further and the xylene is removed by distillation. The residue is the acylated nitrogen compound.

EXAMPLE 55 A high molecular weight mono-carboxylic acid is prepared by telomerizing ethylene with carbon tetrachloride to a telomer having an average of 35 ethylene radicals per molecule and hydrolyzing the telomer to the corresponding acid in accordance with the procedure described in British Patent No. 581,899. A mixture of 1.5 equivalent of the acid and 0.75 equivalent of amino-propyl octylamine is mixed with twice its volume of a mineral oil and twice its volume of xylene. The resulting mixture is heated at the reflux temperature until no more water is removed by azeotropic distillation. Xylene is then removed by distillation under reduced pressure and the residue is filtered.

EXAMPLE 5 6 A mixture of 2000 grams of mineral oil, 3 equivalents of trimethylene diamine and 3 equivalents of a hi P l c ar We ght t icarboxylic acid prepared by the reaction of a brominated poly(1-hexene) having a molecular weight of 2000 and a bromine content of 4% by Weight of 2-pentene-1,3,5-tricarboxylic acid (prepared by dehydration of citric acid) is heated at 150 C. for 20 hours. The residue is filtered to give a homogeneous mineral oil solution of the acylated nitrogen product.

EXAMPLE 57 An equi-molar mixture of Z-aminoethyl morpholine and a mono-carboxylic acid (prepared by the reaction of ketene with a brominated poly(1-octene) having a molecular weight of 1500 and one atom of bromine per mole cule) is diluted with three times its volume of xylene. The resulting mixture is heated at the reflux temperature until no more water is removed by distillation. The residue is an xylene solution of the acylated nitrogen compound.

EXAMPLE 58 A mixture of 1 equivalent of menthane diamine and 1 equivalent of a high molecular glutaric acid-ester (prepared by the reaction of silver with an equi-molar mixture of beta-iodopropanoic acid and alpha-iodo derivative of the methyl ester of the mono-carboxylic acid of the preceding example) is diluted with an equal weight of a mineral oil and the resulting solution is heated at 180 C. until no more water distiils. The residue is then filtered.

EXAMPLE 59 A high molecular weight dicarboxylic acid is prepared by reacting two moles of the omega-bromo derivative of the hexapentacontanoic acid of the preceding example with one mole of zinc. The dicarboxylic acid is then treated with 2 equivalents of ethylene diamine to produce a diamide.

EXAMPLE 61 A mixture of 1 equivalent of 1-aminoethyl-2-octadecylimidazoline with 1 equivalent of the high molecular weight monocarboxylic acid of Example 55 is mixed with twice its volume of diphenyl oxide. The resulting mixture is heated at the reflux temperature until no more water distills. The residue is then filtered.

EXAMPLE 62 A product is obtained by the procedure described in the preceding example except that N,N'-di-n-butyl-p-phenylenediamine (1 equivalent) is used in lieu of the imidazoline used.

EXAMPLE 63 To a solution of 1 equivalent of di-methyl ester of a polyethylene (molecular weight of l500)-substituted malonic acid in 5000 grams of xylene, there is added 1 mole of melamine at 60 C. The resulting mixture is heated at the reflux temperature for 25 hours. The residue is mixed with 2000 grams of mineral oil and xylene is removed by heating the oil solution to 180 C./20 mm.

EXAMPLE 64 A product is obtained by the procedure of Example 1, except that pyrrolydine (1 equivalent) is used in lieu of the diethylene triamine used.

18 EXAMPLE 65 A product is obtained by the procedure of Example 1, except that hexahydro-1,3,5-triazine (1 equivalent) is used in lieu of the diethylene triamine used.

EXAMPLE 66 A product is obtained by the procedure of Example 1, except that 1,3,4-dithiazolidine (1 equivalent) is used in lieu of the diethylene triamine used.

EXAMPLE 67 A product is obtained by the procedure of Example 1, except that hexamethylene tetramine (2 equivalents) is used in lieu of the diethylene triamine used.

EXAMPLE 68 A product is obtained by the procedure of Example 1, except that tripentylene tetramine (3 equivalents) is used in lieu of the diethylene triamine used.

EXAMPLE 69 An equi-molar mixture of the polyisobutene-substituted succinic anhydride of Example 1 and N-octyl thiourea is diluted with an equal volume of xylene. The resulting mixture is heated at the reflux temperature for 30 hours. The residue is an xylene solution of the product.

EXAMPLE 70 A product is obtained by the procedure of Example 69 except that oleylamide is used in lieu of the thiourea used.

EXAMPLE 71 A product is obtained by the procedure of Example 69 except that 1,3-diphenyl guanidine is used in lieu of the thiourea used.

EXAMPLE 72 A product is obtained by the procedure of Example 69 except that octadecamidine is used in lieu of the thiourea used.

EXAMPLE 73 A product is obtained by the procedure of Example 69 except that guanylurea is used in lieu of the thiourea used.

EXAMPLE 74 To a mixture of 396 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 282 grams of mineral oil there was added 34 grams of N-methyltrimethylene diamine at 60 C. within a period of one hour. The mixture was blown with nitrogen at 150- 155 C. for 5 hours. The residue Was found to have a nitrogen content of 1.41%.

EXAMPLE A mixture of 308 grams of mineral oil, 400 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 70 grams of N-(Z-ethylhexyl)-trimethylene diamine was prepared at 60 C. The mixture was heated to 250 C. and wasthen blown with nitrogen at C. for 5 hours. The residue had a nitrogen content EXAMPLE 76 A mixture of 386 grams of mineral oil, 528 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 59 grams of N-(2-hydroxyethyl)-trimethylenediamine was prepared at 60 C. The mixture was blown with nitrogen at 150-155 C. for 5 hours. The residue had a nitrogen content of 1.56%

EXAMPLE 77 A mixture of 185 grams of mineral oil, 330 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 88.5 grams of 1,4-bis(2-hydroxypropyl)-2- methyl piperazine was prepared at 60 C. The mixture was heated at 180-276 C./40 mm. for 14.5 hours. The residue had a nitrogen content of 1.12%.

1 9 EXAMPLE 7% To a mixture of 314 grams of mineral oil and 430 grams of the polyisobutene-substituted succinic anhydride of Example 1 there was added at 60 C., 49 grams of 1-(Z-hydroxyethyl)piperazine. The mixture was heated to 150 C. and blown with nitrogen at this temperature for hours. The residue had a nitrogen content of 1.38%.

EXAMPLE 79 A mixture of 382 grams of mineral oil, 528 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 53 grams of 1-methyl-4-(3-aminopropyl)- piperazine was prepared at 60 C., heated to 150 C., and blown with nitrogen at 150155 C. for 5 hours. The residue had a nitrogen content of 1.57%.

EXAMPLE 80 To a mixture of 800 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 175 grams of toluene there was added 77 grams of a commercial mixture of alkylene amines and hydroxy alkyl-Substituted alkylene amines consisting of approximately 2% (by weight) of diethylene triamine, 36% of 1-(2-aminoethyl) piperazine, 11% of 1-(2-hydroxyethyl)piperazine, 11% of N-(Z-hydroxyethyl)ethylenediamine, and 40% of higher homologues obtained as a result of condensation of the above-indicated amine components. The resulting mixture was heated at the reflux temperature for 16.5 hours whereupon 12 cc. of water was collected as the distillate. The residue was then heated to 160 C./25 mm. and diluted with 570 grams of mineral oil. The final product was found to have a nitrogen content of 1.57%.

EXAMPLE 81 A product is obtained by the procedure of Example 69 except that an equimolar mixture of ammonia and bis(2- hydroxyethyl) amine is used in lieu of the thiourea used.

EXAMPLE 82 A product is obtained by the procedure of Example 69 except that an equimolar mixture of benzidine is used in lieu of the thiourea used.

EXAMPLE 83 An alkenyl succinic anhydride in which the alkenyl group has less than 50 carbon atoms is prepared from a polyisobutylene having an average molecular weight of 375. This polymer is chlorinated to a chlorine content of 9.7% and then reacted with maleic anhydride. The resulting polyisobutenyl succinic anhydride has an acid number of 190 and an equivalent weight of 300. The procedure of Example 1 is followed using 1.0 equivalent of this polyisobutenyl succinic anhydride and 1.0 equivalent of Polyamine H. The resulting product is then diluted with mineral oil to a 58% solution therein; the nitrogen content is 3.2%.

EXAMPLE 84 EXAMPLE 85 A polyisobutene having an average molecular weight of 520 (corresponding to 37 carbon atoms) is chlorinated to a chlorine content of 6.25% and then is made to react with an equivalent amount of maleic anhydride to yield a polyisobutene-substituted succinic anhydride having a saponification of 152. To 552 grams (1.5 equivalents) of this anhydride dissolved in 276 grams of mineral oil there is added at 60 C. 63 grams (1.5 equivalents) of Polyamine H portionwise over a period of 1 hour. The resulting mixture is heated for 6 hours at 150 C. and then blown with nitrogen at this temperature for 1 hour. The residue is diluted with grams of mineral oil and the final oil solution is found to have a nitrogen content of 2.1%.

As indicated previously, the acylated nitrogen-containing composition is usually present in lubricating oils in amounts ranging from about 0.1% to about 10% by weight. The optimum amounts for a particular application depend to a large measure upon the type of surface to which the lubricating composition is to be subjected. Thus, for example, lubricating compositions for use in gasoline internal combustion engines may contain from about 0.5% to about 5% of an acylated nitrogen-containing composition, whereas lubricating compositions for use in gears and diesel engines may contain as much as 10% or even more of the additive.

This invention contemplates also the presence of other additives in the lubricating compositions. Such additives include, for example, detergents of the ash-containing type, viscosity index improving agents, pour point depressing agents, anti-foam agents, extreme pressure agents, rust-inhibiting agents, and oxidation and corrosion inhibiting agents.

The ash-containing detergents are exemplified by oilsoluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium, and barium.

The term basic salt is used to designate the metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The commonly employed methods for preparing the basic salts involves heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50 C. and filtering the resulting mass. The use of a promoter in the neutralization step to aid the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance; alcohols such as methanol, 2- propanol, octyl alcohol, Cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; amines such as aniline, phenylenediamine, phenothiazine, phenyl-betanaphthylamine, and dodecylamine. A particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutral- 12mg agent, a phenolic promoter compound, and a small amount of water and carbonating the mixture at an elevated temperature such as 60200 C.

Extreme pressure agents and corrosion-inhibiting and oxidation-inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, bis- (chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized sperm oil, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pen-tyl phenyl phosphite, dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyl-dithiocarbamate, and barium heptylphenyl dithiocarbamate; Group II metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl)phosphorodithioate, cadmium dinonylphosphorodithioate, and zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol.

The lubricating compositions may also contain metal detergent additives in amounts usually within the range of about 0.1% to about 20% by weight. In some applications such as in lubricating marine diesel engines the lubricating compositions may contain as much as 30% of a metal detergent additive. They may also contain extreme pressure addition agents, viscosity index improving agents, and pour point depressing agents, each in amounts within the range of from about 0.1% to about 10%.

The following examples are illustrative of the lubricating compositions of this invention: (all percentages are by Weight).

Exam le A SAE 20 mineral lubricating oil containing 0.5% of the product of Example 1.

Example B SAE 30 mineral lubricating oil containing 0.75% of the product of Example 2 and 0.l% of phosphorus as the barium salt of di-n-nonylphosphorodithioic acid.

Example C SAE 10W-3O mineral lubricating oil containing 0.4% of the product of Example 7.

Example D SAE 90 mineral lubricating oil containing 0.1% of the product of Example 7 and 0.15% of the Zinc salt of an equimolar mixture of di-cyclohexylphosphorodithoic acid and di-isobutyl phosphorodithioic acid.

Example E SAE 30 mineral lubricating oil containing 2% of the product of Example 3.

Example F SAE 20W-30 mineral lubricating oil containing or" the product of Example 14.

Example G SAE 50 mineral lubricating oil containing 3% of the product of Example 36 and 0.1% of phosphorus as the calcium salt of di-hexylphosphorodithioate.

Example I SAE W-30 mineral lubricating oil containing 2% of the product of Example 48, 0.06% of phosphorus as zinc di-n-octylphosphorodithioate, and 1% of sulfate ash as barium mahogany sulfonate.

Example J V SAE 30 mineral lubricating oil containing 5% of the product of Example 59, 0.1% of phosphorus as the zinc a of 60,000 With parts of salt of a mixture of equimolar amounts of di-isopropylphosphorodithioic acid and di-n-decylphosphorodithioic acid, and 2.5% of sulfate ash as a basic barium detergent prepared by carbonating at C. a mixture comprising mineral oil, barium di-dodecylbenzene sulfonate and 1.5 moles of barium hydroxide in the presence of a small amount of water and 0.7 mole of octylphenol as the promoter.

Example K SAE 10W-30 mineral lubricating oil containing 6% of the product of Example 60, 0.075% of phosphorus as zinc di-n-octylphosphorodithioate, and 5% of the barium salt of an acidic composition prepared by the reaction of 1000 parts of a polyisobutene having'a molecular Weight phosphorus pentasulfide at 200 C. and hydrolyzing the product with steam at 150 C.

Example L SAE 10 mineral lubricating oil containing 2% of the product of Example 74, 0.075% of phosphorus as the adduct of zinc di-cyclohexylphosphorodithioate treated with 0.3 mole of ethylene oxide, 2% of sulfurized sperm oil having a sulfur content of 10%, 3.5% of a poly-(alkyl methacrylate) viscosity index improver, 0.02% of a poly- (alkyl methacrylate) pour point depressant, 0.003% of a poly-(alkyl siloxane) anti-foam agent.

Example M SAE 10 mineral lubricating oil containing 1.5 of the product of Example 51, 0.075% of phosphorus as the adduct obtained by heating zinc di-nonylphosphorodithioate with 0.25 mole of 1,2-hexene oxide at 120 C., a sulfurized methyl ester of tall oil acid having a sulfur content of 15%, 6% of a polybutene viscosity index im prover, 0.005% of a poly-(alkyl methacrylate) anti-foam agent, and 0.5 of lard oil.

Example N SAE 20 mineral lubricating oil containing 1.5 of the product of Example 13, 0.5% of di-dodecyl phosphite, 2% of the sulfurized sperm oil having a sulfur content of 9%, a basic calcium detergent prepared by carbonating a mixture comprising mineral oil, calcium mahogany sulfonate and 6 moles of calcium hydroxide in the presence of an equi-molar mixture (10% of the mixture) of methyl alcohol and n-butyl alcohol as the promoter at the reflux temperature.

Example 0 SAE 10 mineral lubricating oil containing 2% of the product of Example 7, 0.07% of phosphorus as zinc diany acid, and a 500% stoichiometrically excess amount of barium hydroxide in the presence of phenol as the promoter at 180 C., 3% of a supplemental ashless detergent prepared by copolymerizing a mixture of 95% (weight) of decyl-methacrylate and 5% (Weight) of diethylamino-ethylacrylate.

Example Q SAE 10 mineral lubricating oil containing 3% of the product of Example 16, 0.075 of phosphorus as the zinc SAE 20 mineral lubricating oil containing 2% of the product of Example 17 and 0.07% of phosphorus as zinc di-n-octylphosphorodithioate.

Example S SAE 30 mineral lubricating oil containing 3% of the product of Example 48 and 0.1% of phosphorus as zinc di- (isobutylphenyl) -phosphorodithioate.

Example T SAE 50 mineral lubricating oil containing 2% of the product of Example 39.

Example U SAE 90 mineral lubricating oil containing 3% of the product of Example 20' and 0.2% of phosphorus as the reaction product of 4 moles of turpentine with 1 mole of phosphorus pentasulfide.

The above lubricants are merely illustrative and the scope of invention includes the use of all of the additives previously illustrated as well as others within the broad concept of this invention described herein.

The utility of the dispersant additives of this invention is shown by the results of an evaluation of the crankcase lubricants used in taxicabs which had been operated for over 50,000 miles each. In this test ten 6-cylinder 1958 Chevrolet cars (with no oil filters) were operated as a fleet of taxicabs. In each case the crankcase lubricant was a solvent refined Mid-Continent petroleum oil having a viscosity of 185 SUS/ 100 F. and a viscosity index of 112, and containing 5.9% by volume of a poly-alkylmethacrylate viscosity index improver and 0.59% by volume of a zinc dialkyl phosphorodithioate (the allcyl groups being isobutyl and a mixture of primary amyl). Crankcase oil drains were taken from each car at oil-change intervals of about 3,000 miles of service and these drains combined. A 30 cc. sample of each of the combined drains was mixed wtih 1% by weight of the dispersant additive to be tested and 2% by weight of water. This mixture then was homogenized, placed in a 100 cc. graduated coneshaped centrifuge tube and centrifuged for two hours at 1500 r.p.m. The various dispersants were evaluated by noting the volume of deposited sediment in terms of cubic centimeters and also the turbidity of the supernatant oil layer. It is apparent that the more effective dispersants will give test resutls which show a minimum of deposited sediment and a relatively hazy supernatant oil layer.

The clarity of the supernatant oil layer was determined by the amount of light transmitted through it from a 3 volt, 0.75 watt incandescent bulb.

The results of these tests are shown in Table I.

TABLE I Drain Oil Deposits Dispersancy Test Result Additive Tested (1% by weight of diluent tree chemicals) Centimeters Turbidity of Oil of Sedi- Layer ment None 0. 3 Clear-translucent.

Prior Art Product of Example 83 0.3 Do.

Product of Example 0.0 Opaque.

Product of Example 3.. 0. Do.

Product of Example 1.. 0.1 Do.

Product of Example 2. 0.1 Heavy haze.

Product of Example 6 0.0 Do.

The dispersant properties of the compositions of this invention may be illustrated also by the results of an oxidation-dispersancy test which is useful as a screening test for determining the effectiveness of the dispersant additive under light-duty service conditions. In this test a 350 cc. sample of a lubricating oil containing the dispersant additive is placed in a 2" x borosilicate tube. A 1%" x 5%" SAE 1020 steel panel is immersed in the oil. The sample then is heated at 300 F. for 48 hours while air is bubbled through the oil at the rate of 10 liters per hour. The oxidized sample is cooled to 120 E, homogenized, allowed to stand at room temperature for 24 hours and then filtered through two layers of No. 1 Whatman filter paper at mm. Hg pressure. The weight of the precipitate, washed with naphtha and dried, is taken as a measure of the effectiveness of the dispersant additive, i.e., the greater this weight of precipitate the less efiective the dispersant.

Two modifications of the above procedure may be employed; both make the test more severe: one consists of extending the test from 48 hours to 96 hours, and the other involves adding 0.5% of water, based on the weight of the test sample, to the oxidized oil before homogenization.

The lubricating oil employed in this test (Table II) was a Mid-Continent conventionally refined petroleum oil having a viscosity of about 200 SUS/ 100 F., and containing 0.001% by weight of iron naphthenate (to promote oxidation).

TABLE II Additive Tested (1.5% by weight of Oxidation-Dispersance Test diluent-free chemical) Result, mg. of deposit 100 ml. of oil tested None 144 o 275 (b) I Do 1, 000 (a, b) PllOl Art Product of Example 83 738 Prior Art Product of Example 84 1, 060 (b) Prior Art Produst of Example 85..-.. 970 (b) Product of Example 1 0 (b) Product of Example 2 0 7 (b) Product of Example 3.. 1.0 (b) Product of Example 4.- 1. 2 (b) Product of Example 5 1. 5 (b) Product of Example 0.7 (b) Product of Examp 0.5 (b) Product of Example 10. 3.2 (b) Product of Example 11... 10.2 (b) Product of Example 12-.. 19. 5 (b) Product of Example 2.7 (b) Product of Example 14 0.3 Product of Example 14 1.2 (b) Product of Example 14 1. 7 (a, b) Product of Example 15 1.3 (b) Product of Example 16.-. 0. 9 (b) Product of Example 38... 0.1 (b) Product of Example 3 0.2 (a, b) Produ t of Example 41.. 0. 8 (b) Product of Example 41.. 1.0 (a, b) Product of Example 40.. 0. 7 (b) Product of Example 40.. 0.8 (a, 1)) Product of Example 35.. 9.1 (b) Product of Examp 0. 1

Product of Example 44.. 17 Product of Example 49 1. 5 (b) Modification (a): 96 hours testing. Modification (b): 0.5% of water used in the test. Further illustration of the usefulness of the products of this invention as dispersants in motor oils was gained from a modified version of the CRC-EX-B Engine Test. This test is recognized in the field as an important test by which lubricants can be evaluated for use under light- 5 duty service conditions. In this particular test the lubricant is used in the crankcase of a 1954 6-cylinder Chevrolet Powerglide engine for 144 hours under recurring cycling conditions, each cycle consisting of:

2 hours at an engine speed of 500125 r.p.m. under zero load at an oil sump temperature of 100125 F.; ai1' fuel ratio of 10: 1;

2 hours at an engine speed of 2500:25 r.p.m. under a load of 40 brake-horepower at an oil sump temperature of 160170 F.; air-fuel ratio of 16:1,

2 hours at an engine speed of 2500i25.r.-p.m. under a load of 40 brake-horsepower at an oil sump temperature of 240 -250 F air-fuel ratio of 16:1.

After completion of the test, the engine is dismantled and various parts of the engine are examined for engine deposits. The lubricant dispersant addition agent is then rated according to (1) the extent of piston ring-filling, (2) the amount of sludge formed in the engine (on a scale of 80-0, 80 being indicative of no sludge and being indicative of extremely heavy sludge), and (3) the total amount of engine deposits, i.e., sludge and varnish, formed in the engine (on -a scale of 100-0, 100 being indicative of no deposits and 0 being indicative of extremely heavy deposits). The results are summarized in Table III.

TABLE III Percent Total Lubricant Tested Piston Sludge Deposit Ring- Rating Rating Filling 1. Lubricant plus 2.33% by weight of Product of Example 7 t. 1 76. 9 95. 7 2. Lubricant plus 2.33% by weight of Product of Example 8 t 0 73.1 91. 3

What is claimed is:

1. A composition comprising an oil-soluble acylated nitrogen compound having within its structure (A) a hydrocarbon-substituted polar group selected from the class consisting of acyl, acylimidoyl and acyloxy radicals other than succinoyl, succinimidoyl and succinoyloxy radicals, wherein the hydrocarbon substituent contains at least about 50 aliphatic carbon atoms and (B) a nitrogen containing group characterized by a nitrogen atom attached directly to said polar group.

2. The composition of claim 1 wherein the polar group is derived from a mono-carboxy acid.

3. The composition of claim 1 wherein the polar group is derived from a tri-carboxy acid.

4. The composition of claim 1 characterized further in that the hydrocarbon substituent is derived from a polymer of an olefin having from 2 to about 8 aliphatic carbon atoms.

5. The composition of claim 1 wherein the nitrogencontaining group has the formula I l! wherein R and R are selected of hydrogen, hydrocarbon,

from the group consisting amino-substituted hydrocarbon, hydroxy-substituted hydrocarbon, alkoxy-substituted hydrocarbon, amino, carbamyl, thiocarbamyl, guanyl, and acylimidoyl radicals.

6. The composition containing group is alkylene polyamine.

7. An oil-soluble acylated nitrogen-containing composition prepared by the process comprising reacting at a temperature between about 80 C. and up to the decomposition temperature 1 equivalent of a high molecular weight acid-producing compound, other than a succinic acid producing compound, having within its structure a high molecular weight oil-solubilizing group having at least about aliphatic carbon atoms and at least one acid-producing group having the structural configuration wherein X is selected from the group consisting of halogen, hydroxyl, hydrocarbon-oxy, and acyl-oxy radicals, with at least about one-half an equivalent amount of a nitrogen-containing compound having within its structure at least one radical having the structural configuration of claim 1 wherein the nitrogenan amino group derived from an 8. The composition of claim 7 wherein the high molecular weight acid-producing compound is a monocarboxy acid-producing compound.

9. The composition of claim 7 wherein the nitrogencontaining compound has the structural formula Bl]! in which structural formula R and R" are selected from the group consisting of hydrogen, hydrocarbon, aminosubstituted hydrocarbon, alkoxy-substituted hydrocarbon, amino, carbamyl, thiocarbamyl, guanyl, and acylimidoyl radicals.

10. The composition of claim 7 wherein the nitrogencontaining compound is an alkylene polyamine.

References Cited UNITED STATES PATENTS 2,638,450 5/1953 White et a1. 260-326 3,004,987 10/1961 Paris et al. 260-3263 ALEX MAZEL, Primary Examiner. JOSE TOVAR, Assistant Examiner.

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Classifications
U.S. Classification544/243, 544/337, 544/182, 548/123, 554/53, 508/232, 544/176, 544/196, 548/215, 508/550, 548/350.1, 544/180, 548/520, 544/171, 554/42, 508/454, 554/56, 554/57
International ClassificationC08F8/46, C07D207/412, C10M133/52, C08F8/14, C07C51/567, C08F8/32, C08F8/30, C10M133/56, C08F26/00, C08G69/02, C10L1/2383, C07D295/04, C08G69/26, C08F210/16, C10L1/22, C07D207/40, C07G99/00
Cooperative ClassificationC10M2215/223, C10M2215/086, C10M2209/084, C10M2219/083, C10M2225/041, C10M2223/047, C10M2207/40, C10M2207/121, C10M2201/02, C10N2240/106, C10M2219/044, C08F8/46, C10N2240/046, C10M2225/04, C10M2215/12, C10N2240/104, C10M2215/222, C10N2210/01, C10M2209/105, C10M2215/042, C10M2217/046, C10M2219/088, C10M2219/104, C08F8/32, C10M2219/09, C10M2215/06, C10M2205/024, C10M2207/34, C10M2215/04, C10N2240/042, C07G17/00, C08F8/20, C10M2217/045, C10M2207/281, C10M2215/082, C10M2215/30, C10N2240/06, C10M133/52, C10M2225/02, C10M2207/122, C10M2215/225, C10M2223/042, C10M2207/282, C10M2217/00, C10N2240/40, C07C255/00, C10M2219/022, C10M2215/10, C10M2215/224, C10M2217/04, C10M2223/12, C10M2215/221, C10N2240/08, C10M2223/065, C10M2223/04, C10M2217/06, C10M2217/026, C10M133/56, C10L1/2383, C10M2215/18, C10M2207/023, C10M2207/286, C10M2219/046, C10M2215/14, C10M2215/26, C10N2240/401, C10M2209/104, C10L1/221, C10M2219/066, C10M2219/068, C10M2219/024, C10N2240/10, C10M2203/06, C08F8/30, C10N2240/101, C10M2217/022, C10M2205/026, C10M2215/22, C10M2221/04, C10M2215/16, C10M2219/108, C10M2207/125, C10M2223/045, C10M2217/044, C10M2207/404, C10M2219/089, C10M2219/087, C10M2225/00, C10M2219/02, C10M2211/08, C10M2207/129, C10M2215/102, C10M2215/044, C10M2207/027, C10M2219/10, C10M2207/04, C10M2219/102, C10N2230/08, C10M2217/02, C10N2240/044, C10M2219/085, C07C51/567, C08G69/26, C10M2217/024, C10M2207/283, C10M2207/028, C10M2219/106, C07D207/412, C10M2219/06, C10M2221/00, C10M2219/082, C10N2210/00, C10M2209/103, C10M2229/041, C10M2215/28, C10M2209/108, C07D295/04, C10M2215/08, C10M2219/064, C10M2215/226
European ClassificationC07C255/00, C08F8/32, C08F8/30, C07C51/567, C10L1/2383, C10M133/52, C10M133/56, C08G69/26, C07D295/04, C10L1/22W, C07G17/00, C07D207/412, C08F8/46, C08F8/20