Búsqueda Imágenes Maps Play YouTube Noticias Gmail Drive Más »
Iniciar sesión
Usuarios de lectores de pantalla: deben hacer clic en este enlace para utilizar el modo de accesibilidad. Este modo tiene las mismas funciones esenciales pero funciona mejor con el lector.

Patentes

  1. Búsqueda avanzada de patentes
Número de publicaciónUS3087936 A
Tipo de publicaciónConcesión
Fecha de publicación30 Abr 1963
Fecha de presentación18 Ago 1961
Fecha de prioridad18 Ago 1961
También publicado comoDE1274776B, DE1644907A1, US3254025
Número de publicaciónUS 3087936 A, US 3087936A, US-A-3087936, US3087936 A, US3087936A
InventoresSuer William M Le
Cesionario originalLubrizol Corp
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos: USPTO, Cesión de USPTO, Espacenet
Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US 3087936 A
Resumen  disponible en
Imágenes(14)
Previous page
Next page
Reclamaciones  disponible en
Descripción  (El texto procesado por OCR puede contener errores)

' aired States of Ghio Fired Aug. 18, 1961, er. No. 132,395

No Drawing.

1t) Claims. (Ci. 2etl326.3)

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

One of the principal problems associated with present day automobile 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 mayonnaiselike 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 eificient 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 similary 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 eflective in solving the detergency problems associated with motor oils at high temperatures they have not been particularly effective 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 used in engines operated at alternating high and low temperatures.

It is another object of this invention to provide improve-d 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 process for preparing oil-soluble nitrogenand boron-containing compositions comprising treating an acylated nitrogen composition characterized by the presence within its structure of (A) a substatnially hydrocar-substituted suc-cinic radical selected from the class consisting of succinoyl, succinimidoyl, and succinoyloxy 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 succinic radical, with a boron compound selected from the class consisting of boron oxide, boron halides, boron acids, and esters of boron acids in an amount to provide from about 0.1 atomic proportion of boron for each mole of said acylated nitrogen composition to about 10 atomic proportions of boron for each atomic proportion of nitrogen of said acylated nitrogen composition.

The substantially hydrocarbon substituent of the acylated nitrogen composition may contain polar groups provided, however, that the polar groups are not present in proportions sufliciently large to alter significantly the hydrocarbon character of the substituent. The polar groups are exemplified by chlor-o, bromo, keto, ethereal, aldehydo, and nitro, etc. The upper limit with respect to the proportion of such polar groups in the substituent is ap proximately 10% based on the Weight of the hydrocarbon portion of the substituent.

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 30 carbon atoms. The especially useful polymers are the polymers of l-monoclefins such as ethylene, propene, 1-butene, isobutene, l-hexene, l-octene, Z-methyl-l-heptene, 3-cvcloheXyl-1-butene, and Z-methyl-S-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-penetne, and 4-octene.

Also useful are the interpolymers of the olefins such as those illustrated above with other interpolymerizable olefinlc 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; 1 octene with l-hexene; 1 heptene with l-pentene;

3-methyl-1-butene with l-octene; 3,3-dimethyl-1-pentene with 1-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 products 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 of olefinic linkages based on the total number of carbon-to-carbon 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; terpolyrner of 95% ofisobutene with 2% of l-butene and 3% of l-hexene; terpolymer of 80% 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 750-6000 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 final products of this invention. The use of such higher molecular weight olefin polymers often is desirable.

The nitrogen-containing group of the acylated nitrogen compositions of this invention is derived from compounds characterized by a radical having the structural configuration 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 polyarnines such as alkylene amines, arylene amines, cyclic polyamines, and the hydroxy-substituted derivatives of such polyamines.

Specific amines of these types are methylamine, N-methylethylamine, N-methyl-octylamine, N-cyclohexyl-aniline, dibutylamine, cyclohexylamine, aniline, di(p -rnethyl phenyl)amine, dodecylamine, octadecylamine, o-phenylenediamine, N,N' di n butyl p phenylenediamine, morpholine, piperazine, tetrahydropyrazine, indole, hexahydro-1,3,5-triazine, 1-H-1,2,4-triazole, melamine, bis- (p-aminophenyl)methane, phenyl-methylenimine, menthanediamine, cyclohexamine, pyrrolidine, 3-amino-5,6- diphenyl 1,2,4 triazine, ethanolamine, diethanolamine, quinonediimine, 1,3-indandiimine, 2-octadecylirnidazoline, 2 phenyl 4 methyl imidazolidine, oxazolidine, and Z-heptyl-oxazolidine.

A preferred source of the nitrogen-containing group H1TT (alkylene-ITT) 11H 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 such amines such as pipe-razines 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 (2 aminopropyl) imidazoline, 4 methylimidazoline, 1,3 bis(2 aminoethyl).imidazoline, pyrimidine, 1-(Z-aminopropyl)piperazine, 1,4-bis(2-aminoetl1yl) piperazine, and Z-methyl-l- (Z-aminobutyl)piperazine. Higher homologues such as are obtained by condensing two or more of the aboveillustrated 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, volume 5, pages 898905, Interscieuce 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 prodthat of tetraethylene pentamine.

Hydroxyalky -substituted alkylene amines, i.e., alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atoms, likewise are contemplated for use herein. The hydroxyalkyl-substituted alkylene amines are preferably those in which the alkyl rgoup 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 (2 hydroxyethyl)piperazine, mono -.hy droxypropyl substituted diethylene triamine, 1,4 bis(2- hydroxypropyl)piperazine, di-hydroxypropyl-substituted tetraethylene pentamine, N-(3-hydroxypropyl)tetramethylene diamine, and Z-heptadecyl-1-(2-hydroxyethyl) imidazoline.

Higher homologues such as are obtained by condensation of the above-illustrated alkylene amines or hydroxy alkyl-substituted alkylene amines through amino radicals or through hydroxy radical-s are likewise useful. It will be appreciated that condensation through amino radicals results in an higher amine accompanied with removal of ammonia and that condensation through the hydroxy radicals results in products containing either linkages accompanied with removal of Water. 7 Other sources of the nitrogen-containing group include ureas, thioureas, hydrazines, guanidines, amidines, amides, thioamides, cyanamides, etc. Specifice examples illustrating such compounds are: hydrazine, phenylhyrazine, N,N'-diphenylhydrazine, octadecylhydrazine, benzoylhydrazine, urea, thiourea, N-butylurea, stearylamide, oleylamide, guanidine, 1,3 diphenylguanidine,

1,2,3 tributylguanidine, benzamidine, octadecamidine, N,N'-dimethylstearamidine, cyanarnide, dicyandiamide, 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 scuccinic radical. It will be apperciated, of course, that the linkage between a nitrogen atom and a succinoyl radical is representative of an amide or an imide structure, that the linkage between a nitrogen atom and a succinirnidoyl radical is representative of an arnidine structure, and that the linkage between a nitrogen atom and a succinoyloxy radical is representative of an ammoniumcarboxylic acid salt structure. Thus, the acylated nitrogen compositions of this invention are characterized by amide, amide-salt, imide, amidine, or salt linkages and in many instances a mixture of such linkages.

A convenient method for preparing the acylated nitrogen compositions comprises reacting a high molecular weight succinic acid-producing compound characterized by the presence within its structure of a high molecular weight oil-solubilizing group having at lea-st about 50 aliphatic carbon atoms and at least one succinic acidproducing group. Such compounds are illustrated by one having the structural configuration wherein R is a subsantially hydrocarbon radical having at least about 50 aliphatic carbon atoms and X is selected from the class consisting of halogen, hydroxy, hydrocarbon-oxy, and acyloxy radicals, with a least about onehalf 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 succinic acid-producing group with the nitrogen-containing radical to result in the direct attachment of the nitrogen atoms to the succinic radical, i.e., succinoyl, succinimidoyl, or succinolyloxy radical. The linkage formed between the nitrogen atom and the succinic 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 acid-producing 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 l1 (i.e., C-ON) but at relatively high temperatures such as above about 80 C. results predominantly in an amide, imide, or amidine linkage u (i.e., C-N or O--N) 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 substantially saturated, aliphatic hydrcarbon-substituted succinic acids and anhydrides are especially preferred for use as the acid-producing reactant of this process for reasons of the particular elfectiveness 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 100200 C. The product from such a reaction is an alkenyl succinic anhydride. The alkenyl group may be hydrogenater 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 olefins or chlorinated hydrocarbons, other 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, di-polyethylene 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 acid halides of the succinic acids can be prepared by the reaction of the acids or their anhydrides with a halogenation agent such as phosphorus tri-bromide, 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 esteri-- fioation 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 nitrogemcontaining group the acylated nitrogen compositions of this inven tion can be derived.

The above process is usually carried out by heating a mixture of the acid-producing compound and the nitrogen-containing reactant at a temperature above C., preferably within the range from about C., to about 250 C. However, when an acid or anhydride is employed in reactions with an amino nitrogen-containing 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 above 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 one-half of a stoichiometrically equivalent amount of the nitrogencontaining reactant is used for each equivalent of the acidproducing 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 nitrogen-containing radicals. Similarly the equivalent weight of the acid-producing compound is based upon the number of the acid-producing radicals defined by the structural configuration ll -O-X Thus, ethylene diamine has two equivalents per mole; amino guanidine has four equivalents per mole; a suc-. cinic 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 equivalents 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 formationof products having predominantly imide linkages. In most instances, the preferred amount of the nitrogen-containing 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 compositions useful in the process 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 weightof 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 15 minutes, and an initial exothermic reaction caused the temperature to rise to 50 C. The mixture then is heated and a Watertoluene azeotrope distilled from the mixture. When no more water would distill the mixture is heated to 150 C. at reduced pressure to remove the toluene. The residue is diluted with 350 grams of mineral oil and this solution is found to have a nitrogen content of 1.6%.

Example 2 V The procedure of Example 1 is repeated using 31 grams (1 equivalent) of ethylene diamine as the amine reactant. The nitrogen content of the resulting product is 1.4%.

Example 3 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 of 1.9%.

V 7 Example 4 The procedure of Example 1 is repeated using 55.0

grams (1.5 equivalents) of triethylene tetramine as the amine reactant. content of 2.9%

The resulting product has a nitrogen Example 5 amine mixture having an average composition corresponding to that of tetraethylene pentamine. 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 4.7%.

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 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 mixture of 300 parts by weight of the polyisobutenyl succinic anhydride and 160 parts by weight of mineral oil there is added at 65-95 C. an equivalent amount (25 parts by weight) of the commercial ethylene amine mixture of-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 1060 grams of mineral oil is heated at 140150 C. for one hour. Nitrogen is bubbled through the mixture at this temperature for four more hours to aid in the removal of water. The residue is diluted with 420 grams of min- .eral oil and this oil solution is found to have a nitrogen content of 1.3%

Example 9 To a solution of 1,000 grams (1.87 equivalents) of the polyisobutenyl succinic anhydride of Example 7, in 500 grams of mineral oil there is added at 85-95 C. 70 grams (1.87 equivalents) of tetraethylene pentarnine. The mixture then is heated at -165 C. for four hours, blowing with nitrogen to aid in the removal of Water. The residue is diluted with 200 grams of mineral oil and the oil solution found to have a nitrogen content of 1.4%.

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 grams of mineral oil there is added portionwise 22 grams (0.52 equivalent) the commercial ethylene amine mixture of Example 5. 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 150 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 the commercial ethylene amine mixture of Example 5. 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 copolyrner is 1.95%. The resulting alkenyl succinic anhydride had an acid number of 54. To a mixture of 228 grams (0.22 equivalent) of an oil solution of this alkenyl succinic anhydride, 58 grams of additional mineral oil, 500 grams of toluene and 9.3 grams (0.22 equivalent) of the commercial ethylene amine mixture of Example 5 is heated at 110120 C. for three hours, water being re moved from an azeotrope with toluene. When all of the water has thus been removed the 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 chlorinated polyisobutylene with maleic anhydride. The chlorinated polyisobutylene has a chlorine content of 2% and an average molecular weight of 11,000. The polyisobutenyl succinic anhydride has an acid number of 48. A mixture of 410 grams (0.35 equivalent) of this anhydride, grams (0.35 equivalent) of the commercial ethylene amine mixture of Example 5 and 500 grams of toluene is heated at reflux temperature for four hours to remove water from an azeotrope with toluene. The toluene then is removed by heating to 150 C./ millimeters. The nitrogen content of the residue is 1.3%.

Example 14 The procedure of Example 5 is repeated except that 0.94 equivalent of the amine 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 the commercial ethylene amine mixture of Example 5. 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. The residue 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 1056 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 (180l90 C.) for 5 hours. A total of 18 grams of Water is collected from the water-toluene azeotrope. The residue is heated to 150 C./20 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 10 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 70105 C. 108 grams (2.55 equivalents) of the commercial ethylene amine mixture of Example 5 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 polyisobutene-substituted succinic anhydride having an acid 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 25% by Weight of diethylene triamine at room temperature and heating the mixture at 110130 C. for 5 hours and then to C./30 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 160 C. for 5 hours while being purged with nitrogen. A total of 6 cc. of water is removed by distillation. The residue has 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 150155 C. for 5 hours until no more 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 C. for 5 hours until no more water distills. The residue is found to have a nitrogen content of 1.45%.

Example 22 To a mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 500 grams of mineral oil there is introduced at 150-160 C. beneath its surface a sufiicient quantity of ammonia for formation of an imide Within a period of 1 hour. The mixture is diluted with 169 grams of mineral oil, heated to 150 C. and filtered. The filtrate is found to have a nitrogen content of 0.77%.

Example 23 A mixture of 286 grams of polyisobutene-substituted succinic anhydride of Example 1, 96 grams of N,N-dibu-tyl ethylene diamine and 252 grams of mineral oil is prepared at 60 C. and heated at 150l65 C. for 5 hours while being purged with nitrogen. The residue is found to have a nitrogen content of 2.24%.

1 1 Example 24 A mixture of 41 7 grams of polyisobutene-substituted succinic anhydride of Example 1, 30 grams of N-(2- aminoethyl) trimethylene diamine and 293 grams of mineral oil is prepared at 60 -80 C. for 5 hours while being purged with nitrogen. The residue is found to have a nitrogen content of 1.51.

Example 25 A mixture of 430 grams of the polyisobutene-substituted succinic anhydride of Example 1, 64 grams of 1,1- (dimethylaminoethyl)-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 piperazine and 356 grams of mineral oil is prepared at 60 C. and then heated at ISO-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 1110 grams of polyisobutene-substituted succinic anhydride of Example 1, 105 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 6080 C. The resulting mixture is heated at 150-155 C. for 5 hours while being purged With nitrogen. The residue is found to have a nitrogen content of 1.72%.

Example 28 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 tri ethylene tetramine and 20% by Weight of diethylene triamine in the presence of 264 grams of potassium hydroxide (85% purity) and 2200 grams of isopropyl alcohol at 8590 C. A mixture of 528 grams of polyisobutene-substituted 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 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 diarnine and 5 00 grams of mineral oil is prepared at 70100 C. and heated at 150-490 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 A polypropylene-substituted succinic anhydride having an acid number of 84 is prepared by the reaction of a chlorinated polypropylene having a chlorine content of 3% and molecular Weight of 1200 with maleic anhydride. A mixture of 813 grams of the polypropylene-substituted succinic anhydride, 50 grams of a commercial ethylene amine mixture having an average composition corre- 12 sponding to that of tetraethylene pentamine and 566 grams of mineral oil is heated at 150 C. for 5 hours. The residue is found to have a nitrogen content of 1.18%.

Example 32 A mixture of 206 grams of N,N'-disecondary-buty1 p-phenylene diamine, 1000 grams of the polyisobutenesubstituted 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 ene pentamine 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 5060 C. The mixture is heated at 6095 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 95 C. The mixture is then heated at 150-485 C. for 6 hours whereupon 14 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 -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-substL tuted succinic anhydride of Example 1, 418 grams of di(3-aminopropoxy ethyl) ether and 500 grams of mineral oil is heated at -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%.

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 1214 carbon atoms and 500 grams of mineral oil is heated at -250 C. for 13 hours while being urged with nitrogen. The reisdue is then heated to 150 C./1 mm., diluted with 337 grams of mineral oil, heated to C. and filtered. The filtrate has a nitrogen content of 0.87%.

Example 38 A mixture of 1000 grams of the polyi-sobutene-substi tuted succinic anhydride of Example 1, 254 grams of aminoguanidine bicarbonate and 500 grams of mineral 13 oil is prepared at 80 C. and heated at 130-165 C. for hours. The residue is mixed with 223 grams of mineral oil, heated to 150 C., and filtered. 'The filtrate has the nitrogen content of 338%.

Example 39 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 178 grams of 2-amino pyridine and 500 grams of mineral oil is heated at 140-175 C. for hours while being purged with nitrogen. A total of 16 grams of water is collected as the distillate. The residue is diluted wtih 273 grams of mineral oil and filtered. The filtrate has a nitrogen content of 2.55%.

Example 40 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 103 grams of 2,6- di-amino-pyridine and 500 grams of mineral oil is heated at 140-180 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 150 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 condensation product of acrolein with ammonia (molar ratio of 1:1) having a nitrogen content of 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 10 hours. 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 l30-135 C. for 11 hours whereupon 2.5 cc. of water is removed as the distill-ate. 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 polyisobutane-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 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 the 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 2000 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-sub-stituted succinic anhydride of Example 1, and 258 grams of di-n-butylamine is heated at 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 melamine and 200 grams of mineral oil is heated at 250 C. for 9 hours and then at 290295C. 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 A mixture of 100 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 67 grams of mineral oil is heated to 50C. To this mixture there is added 59 grams of a 85% aqueous solution of hydrazine hydrate. The mixture is heated at 100 1l0 C. for 1.25 hours, diluted with toluene, and heated at 107 C. until no more water distills. Toluene is removed by distillation. The residue has a nitrogen content of 0.8%.

Example 52 A product is obtained by the procedure of Example 1, except that pyrrolidine (1 equivalent) is used in lieu of the diethylene triamine used.

Example 54 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.

was heated at 180-276 C./40 mm. for 14.5 hours.

15 Example 55 A product is obtained by the procedure of Example 1, except that 1,3,4-dithi-azolidine (1 equivalent) is used in lieu of the diethylene triamine used.

Example 56 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 5 7 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 58 An equi-mol'ar 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 a xylene solution of the product.

Example 59 A product is obtained by the procedure of Example 58 except that oleylamide is used in lieu of the thiourea used.

Example 60 A product is obtained by the procedure of Example 58 except that 1,3-diphenyl guanidine is used in lieu of the thiourea used.

Example 61 A product is obtained by the procedure of Example 58 except that octadecamidine is used in lieu of the thiourea used.

Example 62 A product is obtained by the procedure of Example 58 except that 'guanylurea is used in lieu of the thiourea used.

Example 63 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 64 A mixture of 386 grams of mineral oil, 528 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 59 grams of N-(Z-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 66 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 The residue has a nitrogen content of 1.12%.

1 6 Example 67 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-(2-hydroxyethyl) piperazine. The mixture was heated to C. and blown with nitrogen at this temperature for 5 hours. The residue had a nitrogen content of 1.38%.

Example 68 A mixture of 382 grams of mineral oil, 528 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 53 grams of 14nethyl-4-(3-a-minopropyl) piperazine was prepared at 6 0 C., heated to 150 C., and blown with nitrogen at 150-155 C. for 5 hours. The residue has a nitrogen content of 1.57%.

Example 69 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 hy-droxy 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-(2 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 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 70 A product is obtained by the procedure of Example 58 except that an equimolar mixture of ammonia and bis(2-hydroxyethyl)amine is used in lieu of the thiourea used.

Example 71 A product is obtained by the procedure of Example 58 except that benzidine is used in lieu of the thiourea used.

Example 72 An acylated nitrogen composition is prepared according to the procedure of Example 1 except that the reaction mixture consists of 3880 grams of the polyisobutcnyl succinic anhydride, 376 grams of a mixture of triethylene tetramine and diethylene triamine (75:25 weight ratio), and 2785 grams of mineral oil. The product is found to have a nitrogen content of 2%.

Example 73 Example 74 An acylated nitrogen composition is prepared according to the procedure of Example 31 except that the polyisobutene-substituted succinic anhydride of Example 1 (1 equivalent for 1.5 equivalents of the amine reactant) is substituted for the polypropylene-substituted succinic anhydride used.

Example 75 An acylated nitrogen composition is prepared according to the procedure of Example 31 except that the polyisobutene-substituted succinic anhydride of Example 1,

(1 equivalent for 2 equivalents of the amine reactant) is substituted for the polypropylene-substituted succinic anhydride used.

1 7 Example 76 An acylated nitrogen composition is prepared according to the procedure of Example 4 except that the commercial ethylene amine mixture (1.5 equivalent per equivalent of the anhydride) of Example 7 is substituted for the triethylene tetramine used.

Example 77 An acylated nitrogen composition is prepared according to the procedure of Example 31 except that the polyisobutene-substituted succinic anhydride of Example 1 (1 equivalent for 1 equivalent of the amine reactant) is substituted for the polypropylene-substituted succinic anhydride. The composition is found to have a nitrogen content of 1.5%.

The boron compounds useful in reaction with the acylated nitrogen compositions include boron oxide, boron oxide hydrate, boron trifiuoride, boron tribromide, boron trichloride, boron acids such as boronic acid (e.g., alkyl- B(OH) or aryl-B(OH) boric acid (i.e., H BO tetraboric acid (i.e., H B O metaboric acid (i.e. HBO and esters of such boron acids. The use of complexes of a boron trihalide with ethers, organic acids, inorganic acids, or hydrocarbons is a convenient means of introducing the boron reactant into the reaction mixture. Such complexes are known and are exemplified by boron-trifiuoride-diethyl ester, boron trifluoride-phosphoric acid, boron trichloride-chloroacetic acid, boron tribromide-dioxane, and boron trifluoride-methyl ethyl ether.

Specific examples of boronic acids include methyl boronic acid, phenyl-boronic acid, cyclohexyl boronic acid, p-heptylphenyl boronic acid and dodecyl boronic acid.

The boron acid esters include especially mono-, di-, and tri-organic esters of boric acid with alcohols or phenols such as, e.g., methanol, ethanol, isopropanol, cyclohexanol, cyclopentanol, l-octanol, 2-octanol, dodecanol, behenyl alcohol, oleyl alcohol, stearyl alcohol, benzyl alcohol, 2- butyl cyclohexanol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 2,4-hexanediol, 1,2- cyclohexanediol, 1,3-octanediol, glycerol, pentaerythritol diethylene glycol, carbitol, Cellosolve, triethylene glycol, tripropylene glycol, phenol, naphthol, p-butylphenol, o,pdiheptylphenol, n-cyclohexylphenol, 2,2-bis-(p-hydroxyphenyl) propane, polyisobutene (molecular weight of 1500)-substituted phenol, ethylenechlorohydrin, o-chlorophenol, m-nitrophenol, 6-bromo-octanol, and 7-keto-decanol. Lower alcohols, 1,2-glycols, and 1-3-glycols, i.e., those having less than about 8 carbon atoms are especially useful for preparing the boric acid esters for the purpose of this invention.

Methods for preparing the esters of boron acid are known and disclosed in the art (such as Chemical Reviews, pages 959-1064, volume 56). Thus, one method involves the reaction of boron trichloride with 3 moles of an alcohol or a phenol to result in a tri-organic borate. Another method involves the reaction of boric oxide with an alcohol or a phenol. Another method involves the direct esterification of tetra boric acid with 3 moles of an alcohol or a phenol. Still another method involves the direct esterification of boric acid with a glycol to form, e.g., a cyclic alkylene borate.

The reaction of the acylated nitrogen compositions with the boron compounds can be effected simply by mixing the reactants at the desired temperature. The use of an inert solvent is optional although it is often desirable, especially when a highly viscous or solid reactant is present in the reaction mixture. The inert solvent may be a hydrocarbon such as benzene, toluene, naphtha, cyclohexane, n-hexane, or mineral oil. The temperature of the reaction may be varied within wide ranges. Ordinarily it is preferably between about 50 C. and about 250 C. In some instances it may be 25 C. or even lower. The upper limit of the temperature is the decomposition point of the particular reaction mixture.

The reaction is usually complete within a short period 18 such as 0.5 to 6 hours. After the reaction is complete, the product may be dissolved in the solvent and the resulting solution purified by centrifugation or filtration if it appears to be hazy or contain insoluble substances. Ordinarily the product is sufiiciently pure so that further purification is unnecessary or optional.

The reaction of the acylated nitrogen compositions with the boron compounds results in a product containing boron and substantially all of the nitrogen originally present in the nitrogen reactant. It is believed that the reaction results in the formation of a complex between boron and nitrogen. Such complex may involve in some instances more than one atomic proportion of boron with one atomic proportion of nitrogen and in other instances more than one atomic proportion of nitrogen with one atomic proportion of boron. The nature of the complex is not clearly understood. Evidence appears to indicate that the complex results from a direct linkage between boron and nitrogen and that in most instances, the radicals originally present in the boron and the nitrogen atoms do not take part directly in the complex formation. However, in the case of a boron acid as the reactant, the reaction is often accompanied with the formation of water.

Inasmuch as the precise stoichiometry of the complex formation is not known, the relative proportions of the reactants to be used in the process are based primarily upon the consideration of utility of the products for the purposes of this invention. In this regard, useful products are obtained from reaction mixtures in which the reactants are present in relative proportions as to provide from about 0.1 atomic proportions of boron for each mole of the acylated nitrogen composition used to about 10 atomic proportions of boron for each atomic proportion of nitrogen of said acylated nitrogen composition used. The preferred amounts of reactants are such as to provide from about 0.5 atomic proportion-of boron for each mole of the acylated nitrogen composition to about 2 atomic proportions of boron for each atomic proportion of nitrogen used. To illustrate, the amount of a boron compound having one boron atom per molecule to be used with one mole of an acylated nitrogen composition having five nitrogen atoms per molecule is within the range from about 0.1 mole to about 50 moles, preferably from about 0.5 mole to about 10 moles.

The following examples are illustrative of the process for preparing the nitrogenand boron-containing compositions of this invention.

Example A To 600 grams (1 atomic proportion of nitrogen) of the acylated nitrogen composition prepared according to the process of Example 77 there is added 45.5 grams (0.5 atomic proportion of boron) of boron trifiuoridediethyl other complex (1:1 molar ratio) at 60-75 C. The resulting mixture is heated to 103 C. and .then at C./30 mm. to distill 011 all volatile components. The residue is found to have a nitrogen content of 1.44% and a boron content of 0.49%.

Example B A mixture of 62 grams (1 atomic proportion of boron) of boric acid and 1645 grams (2.35 atomic proportions of nitrogen) of the acylated nitrogen composition obtained by the process of Example 72 is heated at C. in nitrogen atmosphere for 6 hours. The mixture is then filtered and the filtrate is found to have a nitrogen content of 1.94% and a boron content of 0.33%.

Example C An oleyl ester of boric acid is prepared by heating an equi-molar mixture of oleyl alcohol and boric acid in toluene at the reflux temperature while water is removed azeotropically. The reaction mixture is then heated to 150 C./20 mm. and the residue is the ester having a boron content of 3.2% and a saponification number of 62. A mixture of 344 grams (1 atomic proportion of boron) of the ester and 1645 grams (2.35 atomic proportions of nitrogen) of the acylated nitrogen composition obtained by the process of Example 72 is heated at 150 C. for 6 hours and then filtered. The filtrate is found to have a boron content of 0.6% and a nitrogen content of 1.74%.

Example D A mixture of 344 grams (1 atomic proportion of boron) of the oleyl ester of boric acid of Example C and 1112 grams (2.86 atomic proportions of nitrogen) of the acylated nitrogen composition obtained by the proc-' ess of Example 73 is heated at 150 C. for 6 hours and filtered. The filtrate is found to have a nitrogen con tent of 1.94% and a boron content of 0.81%.

Example E Tri-isobutylborate is prepared by heating a mixture of 620 grams moles) of boric acid, 2220 grams (30 moles) of isobutyl alcohol, and 800 grams of toluene at the reflux temperature while water formed during esterifi cation is being removed by azeotropic distillation. The reaction mass is then heated at 100 C./20 mm. to distill off toluene and the borate is recovered by distillation at 105 -1 10 C./20 mm. The distillate is found to have a boron content of 5.2%. A mixture of 57 grams (0.27 atomic proportion of boron), 13 grams of mineral oil, and 1045 grams (1.56 atomic proportions of nitrogen) of the product obtained by the process of Example 74 is heated at 150-160 C. for 3 hours and then blown with nitrogen at 170 C. (no volatile substance is formed). The mixture is then heated to 150 C./20 mm. and the residue is found to have a boron content of 0.39% and a nitrogen content of 1.98%.

Example F Boron trifiuoride (34 grams, 0.5 atomic proportion of boron) is bubbled into 1400 grams (1.5 atomic proportion of nitrogen) of the product prepared according to the process of Example 77 at 80 C. within a period of 3 hours. The resulting mixture is blown with nitrogen at 70-80 C. for 2 hours and diluted with 23 grams of mineral oil. The residue is found to have a boron content of 0.42%, a fluorine content of 1.58%, and a nitrogen content of 1.41%.

Example G A mixture of 31 grams (0.5 atomic proportion of boron) of boric acid and 1175 grams (1.75 atomic proportions of nitrogen) of the acylated nitrogen composition prepared by the process of Example 74 is heated at 150 C. for 3 hours and filtered. The filtrate is found to have a boron content of 0.43% and a nitrogen content of 1.85%.

Example H A complex of phosphoric acid with 3 moles of boron trifiuoride (67.3 grams, 0.62 atomic proportion of boron) is added dropwise to amixture of 1344 grams (1.92 atomic proportions of nitrogen) of the acylated nitrogen composition of Example 74 and 432 grams of mineral oil. An exothermic reaction occurs. The mixture is heatedat 80-90 C. for 0.5 hour and mixed with 520 cc. of benzene. The resulting solution is washed with, successively, 500 cc. of water, a mixture of 500 cc. of water and 250 cc. of isopropyl alcohol, 50 cc. of a saturated sodium chloride solution, and a mixture of 750 cc. of water and 250 cc. isopropyl alcohol. The washed product is heated to 150 C./38'-68 mm. within a period of 6 hours, cooled, and filtered. The filtrate is found to have a nitrogen content of 1.34% and a boron content of 0.1%.

. Example I A mixture of 12 grams (0.38 mole) of sulfur, 124

20 grams (2 atomic proportions of boron) of boric acid, and 1018 grams (2 atomic proportions of nitrogen) of the acylated nitrogen composition of Example 75 is heated at 150 C. for 3 hours and filtered. The filtrate is found to have a nitrogen content of 2.4%, a boron content of 1.68%, and a sulfur content of 0.5%.

Example I The process of Example I is repeated except that thiourea (38 grams, 0.5 mole) is substituted for the sulfur used. The product is found to have a nitrogen content of 3.3%, a sulfur content of 1.44%, and a boron content of 1.75%.

Example K A mixture of 55 grams (0.39 atomic proportion of boron) of boron trifluoride-diethyl ether complex (1:1 molar ratio) and 480 grams (0.77 atomic proportion of nitrogen) of the'product of Example 76 is heated at 80-90 C. for 0.5 hour and then to C./30 mm. The residue is found to have a nitrogen content of 2.08% and a, boron content of 0.76%.

Example L A mixture of 372 (6 atomic proportions of boron) of boric acid and 3111 grams (6'atomic proportions of nitrogen) of the acylated nitrogen composition obtained by the process of Example 75 is heated at C. for 3 hours and then filtered. The filtrate is found to have a boron content of 1.64% and a nitrogen content of 2.56%

Example M Boric acid (124 grams, 2 atomic proportions of boron) is added to the acylated nitrogen composition (556 grams, 1 atomic proportion of nitrogen) obtained ac- "cording to the procedure of Example 75. The resulting mixture is heated at 150 C. for 3.5 hours and filtered at that temperature. The filtrate is found to have a boron compound of 3.23% and a nitrogen content of 2.3%.

Example 0 A mixture of boric acid and the acylated nitrogen composition prepared according to the procedure of Example 17 in relative proportions such as to provide 1 atomic proportion of boron per atomic proportion of nitrogen is diluted with twice its volume of xylene and the resulting mixture heated at 150 C. for 3 hours and filtered. Xylene is removed by heating the filtrate to 150 C./ 0.25 mm. The residue is found to have a boron content of 0.42% and a nitrogen content of 0.44%.

Example P A mixture of boric acid and the acylated nitrogen composition obtained according to the procedure of Example 44 in relative proportions such as to provide 1 atomic proportion of boron per atomic proportion of nitrogen is heated at 150 C. for 3 hours and filtered. The filtrate is found to have a boron content of 0.2%.

Example Q A mixture of boric acid and an acylated nitrogen compositionobtained by the procedure of Example 41 in relative proportions such as to provide 1 atomic proportion of boron per atomic proportion of nitrogen isheated at 21 150 C. for 3 hours and filtered at this temperature. The filtrate is found to have a boron content of 3.1% and a nitrogen content of 4.1%.

Example R A mixture of boron trifiuoride-diethyl ether complex and a polyisobutene-substituted succinimide derived from a polyisobutene having an average molecular weight of 1000 in relative proportions such as to provide 1 atomic proportion of boron per atomic proportion of nitrogen is heated at 150 C. for 3 hours and filtered at this temperature.

Example S A mixture of boric acid and the acylated nitrogen composition obtained by the procedure of Example 37 in relative proportions such as to provide 1 atomic proportion of boron per atomic proportion of nitrogen is heated at 150 C. for 3 hours and filtered.

Example T A mixture of boric acid and the acylated nitrogen composition obtained according to the procedure of Example 25 in relative proportions such as to provide 1 atomic proportion of boron per atomic proportion of nitrogen is heated at 150 C. for 3 hours and filtered.

The nitrogen and boron-containing products of this invention are useful for a wide variety of purposes including pesticides, plasticizers, rust inhibiting agents for treatment of metals, corrosion-inhibiting agents, extreme pressure agents, anti-wear agents, and detergents.

A principal utility of such products is as additives in lubricants. It has been discovered in accordance with this invention that when used for such purpose the effectiveness of the nitrogenand boron-containing products to impart a specific property to a lubricant is closely related to the size of the substantially hydrocarbon substituent in the succinic radical of the acylated nitrogen composition from which such products are derived. More particularly it has been found that products in which the substantially hydrocarbon substitutent contains more than about 50 aliphatic carbon atoms are effective to impart oxidation-inhibiting, corrosion-inhibiting, and detergent properties to a lubricant. It has also been found that the detergent properties of the products diminish sharply vw'th a decrease in the size of the substantially hydrocarbon substituent having less than about 50 aliphatic carbon atoms so that products having less than about 35 aliphatic carbon atoms in this substituent are ineffective as detergent additives in lubricant.

The lubricating oils in which the compositions of this invention are useful as additives may be of synthetic, animal, vegetable, or mineral origin. Ordinarily mineral lubricating oils are preferred by reason of their availability, general excellence, and low cost. For certain applications, oils belonging to one of the other three groups may be preferred. For instance, synthetic polyester oils such as didodecyl adipate and di-Z-ethylhexyl sebacate are often preferred as jet engine lubricants. Normally the lubricating oils preferred will be fluid oils, ranging in viscosity from about 40 Saybolt Universal seconds at 100 F. to about 200 Saybolt Universal seconds at 210 F.

The concentration of the nitrogenand boron-containing compositions as additives in lubricants usually ranges from about 0.1% to about 10% by weight. The optimum concentrations for a particular application depend to a large measure upon the type of service to which the lubricants is to be subjected. Thus, for example, lubricants for use in gasoline internal combustion engines may contain from about 0.5 to about 5% of the additive, whereas lubricating compositions for use in gears in diesel engines may contain as much as or even more of the additive.

This invention contemplates also the presence of other additives in the lubricating compositions. Such additives include, for example, supplemental detergents of the ashcontaining type, viscosity index improving agents, pour point depressing agents, anti-foam agents, extreme pressure agents, rust-inhibiting agents, and supplemental 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 about 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, phenylenediarnine, phenothiazine, phenylbeta-naphthylamine, and dodecylamine. A particularly efiective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent, a phenolic promoter compound, and a small amount of Water and carbonatin g the mixture at an elevated temperature such as 60-200 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, pentyl 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 phosphorodit-hioates 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 the metal detergent additive. They may also contain extreme pressure addition agents, viscosity in- 23... dex improving agents, and pour point depressing agents, each in amounts within the range from about 0.1% to about 10%.

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

Example I SAE 20 mineral lubricating oil containing 0.5% of the product of Example A.

Example ll SAE 30 mineral lubricating oil containing 0.75% of the product of Example B and 0.1% of phosphorus as the barium salt of di-n-nonylphosphorodithioic acid.

Example III SAE 10W-30 mineral lubricating oil containing 0.4% of the product of Example C.

Example IV SAE 90 mineral lubricating oil containing 0.1% of the product of Example D and 0.15% of the Zinc salt of an equimolar mixture of di-cyclohexylphosphorodithioic acid and di-isobuty-l phosphorodithioic acid.

Example V SAE 30 mineral lubricating oil containing 2% of the product of Example M.

Example VI SAE 20W-30 mineral lubricating oil containing of the product of Example M.

Example VII SAE W-30 mineral lubricating oil containing 1.5% of the product of Example E and 0.05% of phosphorus as the Zinc salt of a phosphorodithioic acid prepared by the reaction of phosphorus pentasulfide with a mixtur of 60% (mole) of p-butylphenol and 40% (mole) of npentyl alcohol.

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

Example IX SAE 10W-30 mineral lubricating oil containing 2% of the product of Example G, 0.06% of phosphorus as zinc di-n-octylphosphorodithioate, and 1% of sulfate ash as barium mahogany sultonate.

Example X SAE 30 mineral lubricating oil containing 5% of the product of Example H, 0.1% of phosphorus as the zinc salt of a mixture of equimolar amounts of di-isopropylphosporodithioic acid and di-n-decylphosphorodithioic acid, and 2.5% of sulfate ash as a basic barium detergent prepared by carbonating at 150 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 XI SAE 1OW-30 mineral lubricating oil containing 6% of the product of Example I, 0.075% of phosphorus as zinc di-n-octylphospho-rodithioate, and 5% of the barium salt of an acidic composition prepared by the reaction of 1000 parts of a polyisobutene having a molecular weight of 60,000 with 100 parts of phosphorus pentasulfide at 200 C. and hydrolyzing the product with steam at 150 C.

Example XII SAE 10 mineral lubricating oil containing 2% of the product of Example I, 0.075 of phosphorus as the adduct of zinc di-cyclohexylphosphorodithioate treated with 0.3 mole of ethylene oxide, 2% of a :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 XIII SAE 10 minteral lubricating oil containing 1.5% of the product of Example K, 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 improver, 0.005% of a poly(alkyl methacrylate) anti-foam agent, and 0.5% of lard oil.

Example XIV SAE 10 mineral lubricating oil containing 2% of the product of Example N, 0.07% of phosphorus as zinc dioctylphosphorodithioate, 2% of a barium detergent prepared by neutralizing with barium hydroxide the hydrolyzed reaction product of a polypropylene (molecular weight 2000) with 1 mole of phosphorus pentasulfide and '1 mole of sulfur, 3% of a barium sulfonate detergent prepared by carbonating a mineral oil solution of mahogany 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 diethylaminoethylacrylate.

Example XVI SAE 80 mineral lubricating oil containing 2% of the product of Example M, 0.1% of phosphorus as zinc di-nhexylphosphorodithioate, 10% ot a chlorinated paraffin wax having a chlorine content of 40%, 2% of di-butyl tetrasulfide, 2% of sulfiurized dipentene, 0.2% of oleyl amide, 0.003% of an anti-foam agent, 0.02% of a pour point depressant, and 3% of a viscosity index irnprover.

, Example XVII SAE 10 mineral lubricating oil containing 3% of the product of Example 0, 0.075% of phosphorus as the zinc salt of a phosphorodithioic acid prepared by the reaction of phosphorus pentasulfide with an equimolar mixture of n-butyl alcohol and dodecyl alcohol, 3% of a barium detergent prepared by canbonating a mineral oil solution containing 1 mole of sperm oil, 0. 6 mole of octylphenol, 2 moles of barium oxide, and a small amount of water at 150 C.

Example XVIII SAE 20 mineral lubricating oil containing 2% of the product of Example P and 0. 07% of phosphorus a-s zinc di'moctylphosphorodithioate.

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

Example XX SAE 50 mineral lubricating oil containing 2% of the product of Example R.

25 product of Example S 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 effect veness of the nitrogenand boron-containing compositions as additives in lubricants to impart oxidationinhibiting, corrosion-inhibiting, and detergent properties is illustrated by the results obtained from an inhibitiondetergency test in which a 350 cc. sample of a lubricant containing 0.001% of iron naphthenate and 1.5% by weight of the additive vto be tested is heated at 300 F. for 48 hours in a 2 x 15 lborosilicate tube. A clean copperlead bearing is immersed in the lubricant along with an SAE 1020 steel test panel. Air is bubbled through the lubricant at the rate of 10 liters per hour. The oxidized sample is allowed to cool to 122 F. whereupon 0.5% (by volume) of water is added and dispersed into the sample. The sample is allowed to stand for 15 hours at room temperature and then filtered through dry No. 1 Whatman paper (double thickness) under slightly reduced pressure. The precipitant is washed with naphtha to constant weight and reported as milligrams of sludge per 100 ml. of oil. The bearing is scrubbed with naphtha, dried, and weighed, and the bearing weight change is reported in milligrams. The viscosity at 100 F. and 210 F. of the lubricant before and after the test is noted. Thus, the quantity of sludge is an indication of the ability of the additive to prevent the formation of harmful deposits; the bearing weight change is an indication of the corrosiveness of the lubricant; and the viscosity change of the lubricant is an indication of the oxidation resistance of the lubricant. The lubricant base employed in the test is a Mid-Continent, conventionally refined mineral oil having a viscosity of about 200 Saybolt Universal seconds at 100 F. The results of the test are summarized in Table I below.

Further illustration of the usefulness of the additive of this invention in lubricants is gained from a modified version (the modification consists of extending the test period from the usual 96 hours to 144 hours) of the CRC-EX3 engine test. This test is recognized in the field as an important test by which lubricants can be evaluated for use under light-duty service conditions. In this particular test the lubricant is used in the crankcase of a 1954 6-cylinder Chevrolet Powerglide engine operated for 144 hours under recurring cycling conditions, each cycle consisting of 2 hours at an engine speed of 500:25 r.p.m. under load and at an oil sump temperature of 100-125 F. and air fuel ratio of 10:1; 2 hours at an engine speed of 2500125 r.p.m. under a load of 40 brake-horse power and at an oil sump temperature of ISO-470 F. and air-fuel ratio of 16:1; and 2 hours at an engine speed of 2500:25 r.p.m. under a load of 40 brakehorsepower and at an oil sump temperature of 240- 250 F. and air-fuel ratio of 16: 1.

Table I Bearing Sludge Viscosity Increase Weight (milli- Additive (1.5% by weight of change grams per diluent-free chemical) (milli- 100 ml. of

grams) Lubri- 100 F. 210 F. cant) Percent Percent None 13. 2 3. 1 53. 1, 145 The acylated nitrogen com positions from which the N and B-containing additives are derived 30 20 100 Product of Example F 1. 3 0.9 13. 9 1. 8 Product of Example A 11.1 2. 8 +0. 9 2.0 Product of Example K 8. 9 2. 1 +3.3 2. 4 Product of Example N 11.2 4. 1 -1. 6 18. 7 Product of Example Q 15. 2 3. 2 -1. 7 60 After completion of the test the engine is dismantled and various parts of the engine are examined for deposit. The lubricant 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 -0, 80 being indicative of no sludge and 0 being indicative of extremely heavy sludge), and 3) the total amount of deposits, i.e., sludge and varnish, formed in the engine (on a scale of -0, 100 being indicative of no deposit and 0 being indicative of extremely heavy deposits). The lubricant used in the test comprises .an SAE 20 mineral .oil containing 1.41% by weight of the product of Example L. The lubricant is found to pass the test with the following result: ring filling, 1%; sludge rating, 75.3; total deposit rating, 93.4.

The efficacy of the nitrogen and boron-containing compositions as additives in lubricants for use under conditions of high speed .and high temperature operation is shown by the results of an engine test carried out in accordance with US. Army Ordnance tentative specification AXS-LSSI. This is known as the Caterpillar ORC- L-ll engine test and the particular test to which the lubricant is subjected is a modification of test, the modification consisting of the use of 'a fuel having a sulfur content of 1% (significantly higher than that of the specified fuel). In this test the lubricant is used in the crankcase of the 4-stroke diesel engine having a 5%" x 8" stroke and a compression ratio of 15 to 1 which is operated for 4 80 hours under the following conditions; speed, 100 r.p.m.;

. BTU input per minute, 2900- 5000; load, 20 brake-horsepower; water jacket outlet temperature, -180 'F.; and oil temperature, 145-150 F. The lubricant is evaluated in terms of 1) the piston cleanliness rating on a scale of 0-100 (100 being perfectly clean and 0 representing maximum deposit) and (2) percent ring filling. A lubricant comprising a SAE 10W-30 mineral oil containing 2% by Weight of the product of Example L is found to pass this test with the following result: ring filling, 19%; piston cleanliness, 96.0.

The eifectiveness of the nitrogenand boron-containing compositions of this invention as additives in lubricants for internal combustion engines is evaluated further by the CRCL4545 engine test. This test involves the operation of a 6-cylinder gasoline automobile engine for 36 hours under the following conditions: engine speed, 3150 r.p.m.; engine load, 30 brake-horsepower; jacket coolant temperature, outlet 200 F., inlet F.; oil sump temperature, 265 F.; and air-fuel ratio, 14.521. The lubricant is rated in terms of the weight loss of bearings, the cleanliness of the pistons and the overall varnish and sludge deposits on the various parts of the engine. By this test, a lubricant comprising a SAE 10W-3O mineral oil containing 2.08% by weight of the product of Example L is found to pass the test with the following results: piston cleanliness rating of 9.5 10 being perfectly clean), overall varnish and sludge rating of 96.7 (100 being perfectly clean), and an average weight loss per bearing of 2.5 milligrams.

The utility of the nitrogenand boron-containing compositions of this invention as additives in lubricants for use in 2-cycle internal combustion engines illustrated by the results of an engine test in which a 7-horsepower chain saw engine (McCulloch model No. 1-80) is operated for 25 hours under the following recurring cycling conditions, each cycle consisting of 15 minutes at zero load and 1800-2200 rpm. and 5 minutes at adjustable load and 5000 rpm. The lubricant comprises a SAE 30 mineral oil containing 7% by volume of the product of Example M and is incorporated in the fuel mixture consisting of 20 parts by volume of a leaded gasoline having an octane number of 95 and 1 part by volume of the lubricant. The lubricant is found to give by this test a piston varnish rating of 7.0 (on a scale of 0 10, 10 being indicative of no varnish and 0 being indicative of extremely heavy varnish) and a crankcase cover varnish rating of 10.0 (on the same scale as above) whereas the base 27 oil, i.e., SAE 30 mineral oil, gives a piston varnish rating of 2.5 and a crankcase cover varnish rating of 8.

What is claimed is:

'1. A process for preparing oil-soluble nitrogenand boron-containing compositions comprising forming an acylated nitrogen intermediate by the reaction at a temperature within the range of from about 80 to about 250 C., of a substantially aliphatic olefin polymer-substituted succinic acid-producing compound having at least about 50 aliphatic carbon atoms in the polymer substituent with at least about one-half equivalent of an amine, for each equivalent of the acid-producing compound used, selected from the class consisting of alkylene amines and hydroxy-substituted \alkylene amines, and reacting, at a temperature between about 50 C. and about 250 C., said acylated nitrogen intermediate with a boron compound selected from the class consisting of boron oxide, boron halide, boron acids, and esters of boron acids in an amount to provide from about 0.1 atomic proportion of boron for each mole of said acylated nitrogen intermediate to about atomic proportions of boron for each atomic proportion of nitrogen of said acylated nitrogen intermediate.

2. A process of claim 1 wherein the polymer substituent of the succinic acid-producing compound is derived from a polyisobutene having an average molecular weight within the range from about 700 to about 5000.

3. The process of claim 1 wherein the amine is a polyethylene polyamine.

4. The process of claim 1 wherein the boron compound is boric acid.

5. An oil-soluble nitrogenand boron-containing composition prepared by the process comprising forming an acylated nitrogen intermediate by the reaction at a temperature within the range of from about 80 C. to about 250 C., of a substantially aliphatic olefin polymer-substituted succinic acid-producing compound having at least about 50 aliphatic carbon atoms in the polymer substituent with at least about one-half equivalent of an amine for each equivalent of acid-producing compound used, selected from the class consisting of alkylene amines and hydroxy-substituted alkylene amines, and reacting at a temperature between about C. and about 250 C. said acylated nitrogen intermediate with a boron compound selected from the class consisting of boron oxide, boron halide, boron acids, and esters of boron acids in an amount to provide from about 0.1 atomic proportion of boron for each mole of said acylated nitrogen intermediate to about 10 atomic proportions of boron for each atomic proportion of nitrogen of said acylated nitrogen intermediate.

6'. The oil-soluble nitrogenand boron-containing composition of claim 5 wherein the polymer substituent of the succinic acid-producing compound is derived from a polymer of isobutene.

7. The oil-soluble nitrogenand boron-containing composition of claim 5 wherein the polymer substituent of the succinic acid-producing compound is derived from a polyisobutene having an average molecular weight within the range of from about 700' to about 5000.

8. The oil-soluble nitrogen, and boron-containing composition of claim 5 wherein the amine is a polyethylene polyamine.

9. The oil-soluble nitrogenand boron-containing composition of claim 5 wherein the boron compound is boric acid.

10. The oil-soluble nitrogenand boron-containing composition of claim 5 wherein the boron compound is boron trifluoride.

References Cited in the file of this patent UNITED STATES PATENTS 2,052,192 Piggott Aug. 25, 1936 2,216,618 Katz Oct. 1, 1940 2,234,581 Rosen Mar. 11, 1941 2,422,278 Young et a1 June 17, 1947 2,611,746 Kipp Sept. 23, 1952 3,000,916 Klass et al. Sept. 19, 1961 3,018,250 Anderson et al Jan. 23, 1962 3,018,291 Anderson et a1 Jan. 23, 1962

Citas de patentes
Patente citada Fecha de presentación Fecha de publicación Solicitante Título
US2052192 *23 Oct 193525 Ago 1936Ici LtdBoric acid esters
US2216618 *10 Ago 19391 Oct 1940Jacob KatzSurface active anionic boric acid ester compounds of amino alcohols
US2234581 *30 Sep 193711 Mar 1941Standard Oil Dev CoHydrocarbon composition containing organic boron compounds
US2422278 *1 Dic 194317 Jun 1947Standard Oil Dev CoLubricating oil composition
US2611746 *17 Dic 194923 Sep 1952Aluminum Co Of AmericaLubricating composition
US3000916 *3 Jun 195819 Sep 1961Standard Oil CoComposition of matter prepared by reacting polymerized linoleic acid with an amine and subsequently reacting the mixture with boric acid
US3018250 *24 Ago 195923 Ene 1962California Research CorpLubricating oil compositions containing nu-dialkylaminoalkyl alkenyl succinimides
US3018291 *24 Ago 195923 Ene 1962California Research CorpNu-dialkylaminoalkyl alkenyl succinimides
Citada por
Patente citante Fecha de presentación Fecha de publicación Solicitante Título
US3163603 *11 Dic 196329 Dic 1964Lubrizol CorpAmide and imide derivatives of metal salts of substituted succinic acids
US3188307 *13 Abr 19628 Jun 1965Pure Oil CoAlkenyl-n-sulfo-oxy-hydrocarbon-imides
US3189544 *19 Dic 196215 Jun 1965Shell Oil CoNon-ash-containing lubricating oil composition
US3194812 *31 Ago 196213 Jul 1965Lubrizol CorpHigh molecular weight alkenyl-n-para amino-phenyl succinimide
US3194813 *18 Oct 196213 Jul 1965Lubrizol CorpHigh molecular weight alkenyl-n-omega amino hexylsuccinimide
US3194814 *18 Oct 196213 Jul 1965Lubrizol CorpHigh molecular weight alkenyl-n-allyl succinimide
US3231587 *7 Jun 196025 Ene 1966Lubrizol CorpProcess for the preparation of substituted succinic acid compounds
US3243371 *10 Dic 196229 Mar 1966Shell Oil CoLubricating composition
US3280034 *30 Sep 196318 Oct 1966Monsanto CoAlkenylsuccinimido alkyl-substituted imidazolidines and related materials
US3281357 *2 Dic 196425 Oct 1966Lubrizol CorpProcess for preparing nitrogen and aluminum containing compositions
US3281428 *29 Abr 196325 Oct 1966Lubrizol CorpReaction product of certain acylated nitrogen containing intermediates and a boron compound
US3282955 *29 Abr 19631 Nov 1966Lubrizol CorpReaction products of acylated nitrogen intermediates and a boron compound
US3284409 *22 Jun 19658 Nov 1966Lubrizol CorpSubstituted succinic acid-boron-alkylene amine phosphatide derived additive and lubricating oil containing same
US3284410 *22 Jun 19658 Nov 1966Lubrizol CorpSubstituted succinic acid-boron-alkylene amine-cyanamido derived additive and lubricating oil containing same
US3294684 *11 Jul 196327 Dic 1966Standard Oil CoLubricant compositions containing detergency additives
US3306908 *26 Dic 196328 Feb 1967Lubrizol CorpReaction products of high molecular weight hydrocarbon succinic compounds, amines and heavy metal compounds
US3311558 *24 Nov 196428 Mar 1967Rohm & HaasN-alkylmorpholinone esters of alkenylsuccinic anhydrides
US3322670 *26 Ago 196330 May 1967Standard Oil CoDetergent-dispersant lubricant additive having anti-rust and anti-wear properties
US3338832 *28 Mar 196629 Ago 1967Lubrizol CorpLubricating oil containing reaction product of certain acylated nitrogen containing intermediates and a boron compound
US3338834 *19 Nov 196529 Ago 1967Chevron ResProcess for preparing nitrogen and boron-containing lubricating oil additives
US3340190 *1 Jun 19655 Sep 1967Standard Oil CoRailway diesel oil
US3344069 *1 Jul 196526 Sep 1967Lubrizol CorpLubricant additive and lubricant containing same
US3367943 *1 Nov 19636 Feb 1968Exxon Research Engineering CoProcess for preparing oil soluble additives which comprises reacting a c2 to c5 alkylene oxide with (a) reaction product of an alkenylsuccinic anhydride and an aliphaticpolyamine (b) reaction product of alkenylsuccinic anhydride, a c1 to c30 aliphatic hydrocarbon carboxylic acid and an aliphatic polyamine
US3385791 *15 Sep 196728 May 1968Standard Oil CoLubricant oil composition
US3442808 *1 Nov 19666 May 1969Standard Oil CoLubricating oil additives
US3446808 *25 May 196427 May 1969Universal Oil Prod CoBorates of n-hydroxyalkyl-nitrogen-heterocyclic saturated compounds
US3449362 *8 Mar 196510 Jun 1969Standard Oil CoAlkenyl hydrocarbon substituted succinimides of polyamino ureas and their boron-containing derivatives
US3455831 *27 Sep 196315 Jul 1969Monsanto CoImines containing a polyalkenylsuccinic anhydride substituent
US3458530 *6 May 196329 Jul 1969Exxon Research Engineering CoMulti-purpose polyalkenyl succinic acid derivative
US3491025 *22 Ene 196820 Ene 1970Standard Oil CoMineral oil solutions of alkenyl substituted bis-succinimide of polyalkylene polyamino diamide from polyalkylene amine-urea condensation product
US3718663 *31 Ago 197027 Feb 1973Standard Oil CoPreparation of oil-soluble boron derivatives of an alkylene polyamine-urea or thiourea-succinic anhydride addition product
US3892671 *25 Ago 19721 Jul 1975Exxon Research Engineering CoLubricant containing dispersant-pour depressant polymer
US3903151 *4 Feb 19742 Sep 1975Chevron ResReaction products of alkali metal meborate and hydrocarbon substituted succinimide
US3950341 *9 Abr 197413 Abr 1976Toa Nenryo Kogyo Kabushiki KaishaReaction product of a polyalkenyl succinic acid or its anhydride, a hindered alcohol and an amine
US3991056 *5 Dic 19759 Nov 1976Toa Nenryo Kogyo Kabushiki KaishaAshless detergent dispersant
US4025445 *15 Dic 197524 May 1977Texaco Inc.Boron amide lubricating oil additive
US4059536 *27 Mar 197522 Nov 1977Institut Francais Du PetroleImproved process for preparing superbasic detergent additives
US4080303 *22 Jul 197421 Mar 1978The Lubrizol CorporationViscosity improver
US4092127 *20 Dic 197630 May 1978Exxon Research & Engineering Co.Anti-dieseling additive for spark ignition engines
US4097389 *19 Jul 197627 Jun 1978Mobil Oil CorporationNovel amino alcohol reaction products and compositions containing the same
US4184851 *18 Dic 197822 Ene 1980Exxon Research & Engineering Co.Borated derivatives of hydrocarbon substituted succinamic acids and/or acid salts thereof are flow improvers for middle distillate fuel oils (PT-364)
US4295983 *12 Jun 198020 Oct 1981Ethyl CorporationLubricating oil composition containing boronated N-hydroxymethyl succinimide friction reducers
US4338205 *25 Ago 19806 Jul 1982Exxon Research & Engineering Co.Lubricating oil with improved diesel dispersancy
US4368133 *25 Feb 198111 Ene 1983The Lubrizol CorporationHydraulic fluids
US4414125 *1 Dic 19808 Nov 1983Chemische Werke Huels AktiengesellschaftAlkali metal or amine salts of a mixture of 2- and 3-alkyladipic acids as corrosion inhibitors
US4447348 *4 Mar 19828 May 1984The Lubrizol CorporationCarboxylic solubilizer/surfactant combinations and aqueous compositions containing same
US4448703 *4 Mar 198215 May 1984The Lubrizol CorporationSolubilizer is reaction product of polycarboxylic acid acylation agent with hydroxyl acrylic amine
US4471091 *9 Ago 198211 Sep 1984The Lubrizol CorporationCombinations of carboxylic acylating agents substituted with olefin polymers of high and low molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
US4486573 *9 Ago 19824 Dic 1984The Lubrizol CorporationOil and fuel additives
US4489194 *9 Ago 198218 Dic 1984The Lubrizol CorporationCarboxylic acylating agents substituted with olefin polymers of high/low molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
US4559155 *12 Mar 198517 Dic 1985The Lubrizol CorporationHydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same
US4564460 *9 Ago 198214 Ene 1986The Lubrizol CorporationHydrocarbyl-substituted carboxylic acylating agent derivative containing combinations, and fuels containing same
US4575526 *12 Mar 198511 Mar 1986The Lubrizol CorporationHydrocarbyl substituted carboxylic acylaging agent derivative containing combinations, and fuels containing same
US4596663 *19 Oct 198424 Jun 1986The Lubrizol CorporationOlefin polymer components reacted with one or more amines, alcohols, or mixtures thereof
US4613342 *16 Oct 198523 Sep 1986The Lubrizol CorporationHydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same
US4637886 *16 Nov 198320 Ene 1987Exxon Research & Engineering Co.Macrocyclic polyamine and polycyclic polyamine multifunctional lubricating oil additives
US4666620 *13 Mar 198619 May 1987The Lubrizol CorporationCarboxylic solubilizer/surfactant combinations and aqueous compositions containing same
US4749505 *8 Jul 19857 Jun 1988Exxon Chemical Patents Inc.Olefin polymer viscosity index improver additive useful in oil compositions
US4755311 *14 Ago 19865 Jul 1988The Lubrizol CorporationPhosphorus-, sulfur- and boron-containing compositions, and lubricant and functional fluid compositions containing same
US4756820 *8 Jul 198612 Jul 1988Betz Laboratories, Inc.Method for retarding corrosion and coke formation and deposition during pyrolytic hydrocarbon processing
US4770803 *3 Jul 198613 Sep 1988The Lubrizol CorporationWater based functional fluids, i.e. lubricants, hydraulic fluids, cutting fluids
US4801390 *28 May 198531 Ene 1989Exxon Research & Engineering Co.Lubricating compositions
US4820432 *24 Jul 198711 Abr 1989Exxon Chemical Patents Inc.Lactone-modified, Mannich base dispersant additives useful in oleaginous compositions
US4855074 *14 Mar 19888 Ago 1989Ethyl Petroleum Additives, Inc.Heating long chain succinimide and benzotriazole
US4863624 *9 Sep 19875 Sep 1989Exxon Chemical Patents Inc.Dispersant additives mixtures for oleaginous compositions
US4866139 *7 Oct 198612 Sep 1989Exxon Chemical Patents Inc.Lactone modified, esterified dispersant additives useful in oleaginous compositions
US4866140 *7 Oct 198612 Sep 1989Exxon Chemical Patents Inc.Oil, fuel additives
US4866141 *7 Oct 198612 Sep 1989Exxon Chemical Patents Inc.Lactone modified, esterfied or aminated additives useful in oleaginous compositions and compositions containing same
US4906394 *7 Oct 19866 Mar 1990Exxon Chemical Patents Inc.Lactone modified mono-or dicarboxylic acid based adduct dispersant compositions
US4925983 *14 Abr 198815 May 1990The Lubrizol CorporationBoronated compounds
US4943382 *6 Abr 198824 Jul 1990Exxon Chemical Patents Inc.Lactone modified dispersant additives useful in oleaginous compositions
US4954276 *31 Ago 19894 Sep 1990Exxon Chemical Patents Inc.Olefin polymer modified by an unsaturated dicarboxylic acid and a hydroxy-amide or hydroxy-ester compound; efficiency; crankcase oil additive
US4954277 *31 Ago 19894 Sep 1990Exxon Chemical Patents Inc.Lactone modified, esterified or aminated additives useful in oleaginous compositions and compositions containing same
US4963275 *6 Abr 198816 Oct 1990Exxon Chemical Patents Inc.Dispersant additives derived from lactone modified amido-amine adducts
US4971711 *9 Ene 198920 Nov 1990Exxon Chemical Patents, Inc.Lactone-modified, mannich base dispersant additives useful in oleaginous compositions
US5032320 *28 Feb 199116 Jul 1991Exxon Chemical Patents Inc.Oil additives
US5041622 *28 Nov 199020 Ago 1991The Lubrizol CorporationThree-step process for making substituted carboxylic acids and derivatives thereof
US5110488 *17 Nov 19895 May 1992The Lubrizol CorporationLubricating compositions containing reduced levels of phosphorus
US5198133 *22 Jun 199230 Mar 1993Ethyl Petroleum Additives, Inc.Modified succinimide or sucinamide dispersants and their production
US5221491 *9 Ago 199122 Jun 1993Exxon Chemical Patents Inc.Two-cycle oil additive
US5225093 *3 Dic 19926 Jul 1993Ethyl Petroleum Additives, Inc.Gear oil additive compositions and gear oils containing the same
US5304315 *15 Abr 199219 Abr 1994Exxon Chemical Patents Inc.Prevention of gel formation in two-cycle oils
US5308521 *28 Sep 19933 May 1994The Lubrizol CorporationLubricant with improved anti-corrosion properties
US5312554 *6 Jul 198917 May 1994Exxon Chemical Patents Inc.Dispersant-detergents with haze resistant mixtures, heat treatment and cooling
US5328619 *21 Jun 199112 Jul 1994Ethyl Petroleum Additives, Inc.Oil additive concentrates and lubricants of enhanced performance capabilities
US5330667 *15 Abr 199219 Jul 1994Exxon Chemical Patents Inc.Two-cycle oil additive
US5334329 *7 Oct 19882 Ago 1994The Lubrizol CorporationLubricant and functional fluid compositions exhibiting improved demulsibility
US5354484 *7 Jun 199011 Oct 1994The Lubrizol CorporationImproved high temperature stability
US5370807 *10 May 19936 Dic 1994Ministero Dell'universita' E Della Ricerca Scientifica E TechnologicaPolymer of an acrylate and a 1,3,2-dioxaborinan-2-yloxy-alkylene acrylate; viscosity index improver; friction modifier
US5389273 *3 Sep 199314 Feb 1995Ethyl Petroleum Additives, Inc.An automatic transmission fluid mixture comprising a base oils , viscosity index promoters, a phosphorus-containing polyisobutylene succinimide or succinamide; wear resistance, high viscosity
US5430105 *22 Nov 19934 Jul 1995Exxon Chemical Patents Inc.Low sediment process for forming borated dispersant
US5439606 *7 Oct 19948 Ago 1995Ethyl Petroleum Additives, Inc.Automatic transmission fluids; preblending a phosdphorus ester and a alkenyl succinimide or succinamide; heating in presence of water to hydrolyze ester
US5451333 *25 Mar 199419 Sep 1995Exxon Chemical Patents Inc.Haze resistant dispersant-detergent compositions
US5490945 *28 Abr 199413 Feb 1996The Lubrizol CorporationLubricating compositions and concentrates
US5498809 *22 May 199512 Mar 1996Exxon Chemical Patents Inc.Terminal ethylvinylidene groups which can be functionalized, dispersants
US5554310 *9 Jun 199410 Sep 1996Exxon Chemical Patents Inc.Trisubstituted unsaturated polymers
US5558802 *14 Sep 199524 Sep 1996Exxon Chemical Patents IncMultigrade crankcase lubricants with low temperature pumpability and low volatility
US5562864 *3 Nov 19948 Oct 1996The Lubrizol CorporationOil with one carboxy derivative formed by acylation of succinic acid and a mixture of overbased salt of carboxylic acid, or acid with sulfonic acid with magnesium or calcium compounds
US5562867 *28 Jun 19958 Oct 1996Exxon Chemical Patents IncBiodegradable two-cycle oil composition
US5583099 *16 May 199610 Dic 1996The Lubrizol CorporationBoronated compounds
US5614480 *25 Jul 199425 Mar 1997The Lubrizol CorporationLubricating compositions and concentrates
US5629434 *25 Sep 199513 May 1997Exxon Chemical Patents IncReaction product of polymer with at least one ethylenic double bond with carbon monoxide and nucleophilic trapping agent; dispersants, viscosity modifiers
US5643859 *17 Jun 19941 Jul 1997Exxon Chemical Patents Inc.Fuel dispersant
US5646098 *13 May 19948 Jul 1997Exxon Chemical Patents IncCarbonyl containing compounds and their derivatives as multi-functional fuel and lube additives
US5646332 *17 Jun 19948 Jul 1997Exxon Chemical Patents Inc.Batch Koch carbonylation process
US5650536 *17 Jun 199422 Jul 1997Exxon Chemical Patents Inc.Continuous process for production of functionalized olefins
US5652201 *11 Jul 199529 Jul 1997Ethyl Petroleum Additives Inc.Lubricating oil compositions and concentrates and the use thereof
US5652202 *15 Ago 199529 Jul 1997Exxon Chemical Patents Inc.Antideposit, ethylene copolymers in admixture with functionalized non-ethylene polymers
US5658862 *19 Ene 199619 Ago 1997Exxon Research And Engineering CompanyContains a boron containing alkenyl succinimide, molybdenum dithiocarbamate and/or molybdenum dithiophosphate, calcium and magnesium salicylate and ethylene copolymer
US5663130 *11 Mar 19962 Sep 1997Exxon Chemical Patents IncPolymers derived from ethylene and 1-butene for use in the preparation of lubricant dispersant additives
US5696064 *23 Ago 19959 Dic 1997Exxon Chemical Patents Inc.From carbon monoxide and a nucleophilic trapping agent
US5698722 *6 Jun 199516 Dic 1997Exxon Chemical Patents Inc.Blend of addition polymer, carbon monoxide and nucleophilic trapping agent
US5703256 *16 Dic 199630 Dic 1997Exxon Chemical Patents Inc.Functionalization of polymers based on Koch chemistry and derivatives thereof
US5717039 *6 Jun 199510 Feb 1998Exxon Chemical Patents Inc.Functionalization of polymers based on Koch chemistry and derivatives thereof
US5756428 *29 Sep 198826 May 1998Exxon Chemical Patents Inc.Oil additive; modified polyolefin
US5767046 *15 May 199716 Jun 1998Exxon Chemical CompanyPrepared by reacting an olefin, carbon monoxide, an acid catalyst and a nucleophilic trapping agent selected from hydroxy- and thiol-containing compounds
US5788722 *30 May 19954 Ago 1998Exxon Chemical Patents IncHigh functionality low molecular weight oil soluble dispersant additives useful in oleaginous compositions
US6008165 *31 Jul 199828 Dic 1999The Lubrizol CorporationAlcohol borate esters and borated dispersants to improve bearing corrosion in engine oils
US6010986 *31 Jul 19984 Ene 2000The Lubrizol CorporationAlcohol borate esters to improve bearing corrosion in engine oils
US6030930 *14 May 199729 Feb 2000Exxon Chemical Patents IncUseful in lubricating oils, and to concentrates containing the oil-soluble dispersant additives
US6051537 *14 Abr 199318 Abr 2000Exxon Chemical Patents IncDispersant additive mixtures for oleaginous compositions
US6127321 *5 Sep 19913 Oct 2000Exxon Chemical Patents IncLubricating oil, metal containing detergent or antirust agent, and oil soluble dispersant comprising the reaction product of an unsaturated acid-modified polyolefin and an amine, alcohol, or amino alcohol; does not cause thickening
US622543724 Jun 19991 May 2001Albemarle CorporationUseful as internal and external sizing agents for paper and paper products
US623165924 Jun 199915 May 2001Albemarle CorporationSizing agents and starting materials for their preparation
US630680222 Abr 199723 Oct 2001Exxon Chemical Patents Inc.Mixed antioxidant composition
US635507425 May 199512 Mar 2002Exxon Chemical Patents IncOil soluble dispersant additives useful in oleaginous compositions
US636213626 Mar 199626 Mar 2002The Lubrizol CorporationCompositions for extending seal life, and lubricants and functional fluids containing the same
US642367014 Mar 200123 Jul 2002Infineum International Ltd.Lubricating oil compositions
US6476096 *13 Jul 20005 Nov 2002Xaar Technology LimitedInk jet printer ink
US648927120 Ago 19963 Dic 2002The Lubrizol CorporationCombination of a sulfur compound and specific phosphorus compounds and their use in lubricating compositions, concentrates and greases
US65732234 Mar 20023 Jun 2003The Lubrizol CorporationLubricating compositions with good thermal stability and demulsibility properties
US662758428 Ene 200230 Sep 2003Ethyl CorporationAutomatic transmission fluid additive comprising reaction product of hydrocarbyl acrylates and dihydrocarbyldithiophosphoric acids
US67341486 Dic 200111 May 2004Infineum International Ltd.Dispersants and lubricating oil compositions containing same
US67437576 Dic 20011 Jun 2004Infineum International Ltd.Dispersants and lubricating oil compositions containing same
US682467117 May 200130 Nov 2004Exxonmobil Chemical Patents Inc.1-decene and 1-dodecene are polymerized using an alcohol promoted boron trifluoride and cocatalysts; lubricants
US68556742 Dic 200215 Feb 2005Infineum International Ltd.Hydroxy aromatic Mannich base condensation products and the use thereof as soot dispersants in lubricating oil compositions
US686991716 Ago 200222 Mar 2005Exxonmobil Chemical Patents Inc.5 cSt poly-alpha-olefin comprising an oligomer of 40-80 % 1-decene and 60-20 % 1-dodecene and a 4 cSt poly-alpha-olefin; prepared by oligomerizing the monomers in the presence of BF3, alcohol and alkyl acetate
US693335120 Jun 200323 Ago 2005Infineum International LimitedProcess for forming polyalkenyl acylating agents
US69496886 Oct 200427 Sep 2005Exxonmobil Chemical Patents Inc.Oligomerization of 1-decene and 1-dodecene, in the presence of boron fluoride and activators as catalysts, then hydrogenation to form lubricants having stability; extreme temperature lubricants
US718279513 Mar 200227 Feb 2007Atton Chemical Intangibles LlcFuel lubricity additives derived from hydrocarbyl succinic anhydrides and hydroxy amines, and middle distillate fuels containing same
US733900720 Jun 20034 Mar 2008Infineum International LimitedReacting a low molecular weight polyalkene such as polyisobutylene with an enophile such as maleic anhydride at high temperature in the presence of a free radical inhibitor and in the absence of halogen, to form products useful per se as and as intermediates for oil, functional fluid and fuel additives
US782060212 Jul 200626 Oct 2010King Industries, Inc.Diarylamine or alkylated phenothiazine as antioxidants; for use in crankcase and transmission
US783395328 Ago 200616 Nov 2010Afton Chemical CorporationDispersant and a base oil containing more than 1.6% by weight of tetracycloparaffins
US787977514 Jul 20061 Feb 2011Afton Chemical CorporationLubricant compositions
US788829913 Ene 200415 Feb 2011Afton Chemical Japan Corp.For use in heavy duty (HD) axle and transmission applications; low odor, high temperature oxidation stability, antiwear protection, copper passivation and synchronizer performance without requiring the use of metal detergents
US790213314 Jul 20068 Mar 2011Afton Chemical CorporationLubricant composition
US79282603 Sep 200819 Abr 2011Afton Chemical CorporationSalt of a sulfur-containing, phosphorus-containing compound, and methods thereof
US794763627 Feb 200424 May 2011Afton Chemical CorporationPower transmission fluids
US80805003 Abr 200820 Dic 2011King Industries, Inc.Amine tungstates and lubricant compositions
US808069928 Ago 200920 Dic 2011Chemtura CorporationTwo-stage process and system for forming high viscosity polyalphaolefins
US815820812 Sep 200817 Abr 2012Osmose, Inc.Method of preserving wood by injecting particulate wood preservative slurry
US82990039 Mar 200630 Oct 2012Afton Chemical CorporationComposition comprising a sulfur-containing, phosphorus-containing compound, and/or its salt, and uses thereof
US840962715 Jul 20092 Abr 2013Osmose, Inc.Particulate wood preservative and method for producing the same
US84152845 Nov 20099 Abr 2013Afton Chemical CorporationOlefin copolymer VI improvers and lubricant compositions and uses thereof
US842058324 Ene 200816 Abr 2013Afton Chemical CorporationOlefin copolymer dispersant VI improver and lubricant compositions and uses thereof
US854631110 Mar 20091 Oct 2013Volkswagen AktiengesellsschaftMethod for lubricating a clutch-only automatic transmission component requiring lubrication
US855775222 Mar 200615 Oct 2013Afton Chemical CorporationLubricating compositions
US856348917 Sep 200822 Oct 2013Chemtura CorporationAlkylated 1,3-benzenediamine compounds and methods for producing same
US858652027 Jun 201219 Nov 2013Exxonmobil Research And Engineering CompanyMethod of improving pour point of lubricating compositions containing polyalkylene glycol mono ethers
US87036661 Jun 201222 Abr 2014Exxonmobil Research And Engineering CompanyLubricant compositions and processes for preparing same
US870366917 Feb 200922 Abr 2014Afton Chemical CorporationUltra-low sulfur clutch-only transmission fluids
US872219813 Abr 201213 May 2014Osmose, Inc.Method of preserving wood by injecting particulate wood preservative slurry
US20110036262 *26 Ago 201017 Feb 2011Advanced Lubrication Technology, Inc.Corrosion Prevention and Friction Reduction Coating and Low Temperature Process
USRE36479 *4 Oct 19964 Ene 2000The Lubrizol CorporationAqueous compositions containing nitrogen-containing salts
CN101072798B8 Dic 200516 Oct 2013卢布里佐尔公司Process of preparation of an additive and its use
DE1301535B *13 Oct 19645 Feb 1970Lubrizol CorpVerfahren zur Herstellung oelloeslicher, stickstoffhaltiger Reaktionsprodukte
DE102008005330A121 Ene 20087 Ago 2008Afton Chemical Corp.Schmiermittelzusammensetzung für Biodieselkraftstoffmotorverwendungen
DE102009001301A13 Mar 200924 Sep 2009Audi AgVerfahren zum Schmieren einer Komponente nur für die Kupplung eines automatischen Getriebes, welche Schmierung erfordert
DE102009012567A111 Mar 20091 Oct 2009Afton Chemical Corp.Getriebeöle mit sehr wenig Schwefel nur für Kupplung
DE102012223638A118 Dic 201227 Jun 2013Infineum International Ltd.Verfahren zur Herabsetzung der Abnahmerate der Basizität einer Schmierölzusammensetzung, die in einem Motor verwendet wird
EP0061346A2 *23 Mar 198229 Sep 1982Edwin Cooper Inc.Dispersant composition for lubricating oil, additive packages and lubricating oil compositions comprising the dispersant ingredients of said composition, a method of imparting dispersancy to a lubricating oil, and ingredients intended for use in a dispersant mixture
EP0167295A2 *4 Jun 19858 Ene 1986Exxon Research And Engineering CompanyImproved lubricating compositions
EP0351964A123 Jun 198924 Ene 1990Exxon Chemical Patents Inc.Synergistic combination of additives useful in power transmitting compositions
EP0399764A121 May 199028 Nov 1990Ethyl Petroleum Additives LimitedLubricant compositions
EP0558835A130 Ene 19928 Sep 1993Albemarle CorporationBiodegradable lubricants and functional fluids
EP0611818A130 Jul 199124 Ago 1994Exxon Chemical Patents Inc.Low pressure derived mixed phosphorous- and sulfur-containing reaction products useful in power transmitting compositions and process for preparing the same
EP0683220A218 May 199522 Nov 1995Ethyl CorporationLubricant additive compositions
EP0695798A22 Ago 19957 Feb 1996The Lubrizol CorporationLubricating compositions, concentrates, and greases containing the combination of an organic polysulfide and an overbased composition or a phosphorus or boron compound
EP1624043A210 Jun 20058 Feb 2006Afton Chemical CorporationPower transmission fluids with enhanced extreme pressure and antiwear characteristics
EP1669436A18 Dic 200514 Jun 2006Afton Chemical CorporationOxidation stable gear oil compositions
EP1728848A121 Abr 20066 Dic 2006Infineum International LimitedUse of unsaturated olefin polymers to improve the compatibility between nitrile rubber seals and lubricating oil compositions
EP1959003A228 Ene 200820 Ago 2008Infineum International LimitedSoot dispersants and lubricating oil compositions containing same
EP2017329A117 Abr 200821 Ene 2009Afton Chemical CorporationEnvironmentally-Friendly Lubricant Compositions
EP2075264A14 Dic 20081 Jul 2009Infineum International LimitedMethod of forming polyalkene substituted carboxylic acid compositions
EP2075315A118 Jul 20081 Jul 2009Infineum International LimitedAdditive Compositions with Michael adducts of N-substituted phenylenediamines
EP2083024A112 Sep 200829 Jul 2009Afton Chemical CorporationOlefin copolymer dispersant VI improver and lubricant compositions and uses thereof
EP2083063A114 Ene 200929 Jul 2009Infineum International LimitedLubricating oil composition
EP2090642A127 Ene 200919 Ago 2009Infineum International LimitedEngine lubrication
EP2116590A12 Feb 200611 Nov 2009Infineum International LimitedSoot dispersants and lubricating oil compositions containing same
EP2161326A15 Sep 200810 Mar 2010Infineum International LimitedLubricating oil compositions
EP2163602A120 Ago 200917 Mar 2010Infineum International LimitedA lubricating oil composition
EP2206764A14 Feb 200914 Jul 2010Infineum International LimitedAniline compounds as ashless TBN sources and lubricating oil compositions containing same
EP2230292A18 Nov 200422 Sep 2010Afton Chemical CorporationMethods of lubricating transmissions
EP2233554A127 Mar 200929 Sep 2010Infineum International LimitedLubricating oil compositions
EP2236590A16 Abr 20096 Oct 2010Infineum International LimitedLubricating oil composition
EP2239314A131 Mar 201013 Oct 2010Infineum International LimitedLubricating oil composition
EP2290038A229 Jul 20102 Mar 2011Infineum International LimitedA lubricating oil composition
EP2290041A229 Jul 20102 Mar 2011Infineum International LimitedA lubricating oil composition
EP2290043A120 Jul 20102 Mar 2011Infineum International LimitedA lubricating oil composition comprising metal dialkyldithiophosphate and carbodiimide
EP2302023A22 Oct 200330 Mar 2011R.T. Vanderbilt Company, Inc.Synergistic organoborate compositions and lubricating compositions containing same
EP2319904A16 Sep 201011 May 2011Infineum International LimitedLubrication and lubricating oil compositions comprising phenylene diamines
EP2325291A120 Oct 201025 May 2011Afton Chemical CorporationOlefin Copolymer VI improvers and lubricant compositions and uses thereof
EP2363454A124 Dic 20107 Sep 2011Infineum International LimitedA lubricating oil composition
EP2365049A129 Jul 201014 Sep 2011Infineum International LimitedUse of a lubricating additive
EP2366761A110 Feb 201121 Sep 2011Infineum International LimitedMorpholine derivatives as ashless TBN sources and lubricating oil compositions containing same
EP2366762A12 Oct 200321 Sep 2011R.T. Vanderbilt Company Inc.Synergistic organoborate compositions and lubricating compositions containing same
EP2371932A19 Mar 20115 Oct 2011Infineum International LimitedA lubricating oil composition
EP2371934A124 Mar 20115 Oct 2011Infineum International LimitedLubricating oil composition
EP2374866A121 Feb 201112 Oct 2011Infineum International LimitedA lubricating oil composition comprising alkoxylated phenol-formaldehyde condensate
EP2390306A115 Nov 201030 Nov 2011Infineum International LimitedA lubricating oil composition
EP2420552A119 Ago 201022 Feb 2012Infineum International LimitedEGR Equipped Diesel Engines and Lubricating Oil Compositions
EP2420553A117 Abr 200822 Feb 2012Afton Chemical CorporationEnvironmentally-Friendly Lubricant Compositions
EP2436753A12 Oct 20034 Abr 2012R.T. Vanderbilt Company Inc.Synergistic organoborate compositions and lubricating compositions containing same
EP2453000A18 Nov 201016 May 2012Infineum International LimitedLubricating Oil Composition comprising a hydrogenated imide derived from a Diels-Alder adduct of maleic anhydride and a furan
EP2457984A120 Oct 201130 May 2012Infineum International LimitedA lubricating oil composition
EP2460870A12 Oct 20036 Jun 2012R.T. Vanderbilt Company, Inc.Synergistic organoborate compositions and lubricating compositions containing same
EP2559748A116 Jul 201220 Feb 2013Infineum International LimitedLubricating oil composition
EP2574656A128 Sep 20113 Abr 2013Infineum International LimitedLubricating oil compositions
EP2584025A121 Oct 201124 Abr 2013Infineum International LimitedLubricating oil composition
EP2620207A230 Oct 200931 Jul 2013Calera CorporationNon-cementitious compositions comprising CO2 sequestering additives
EP2687583A112 Jul 201322 Ene 2014Infineum International LimitedLubricating oil compositions containing sterically hindered amines as ashless TBN sources
EP2692839A116 Jul 20135 Feb 2014Infineum International LimitedA lubricating oil compostion comprising a corrosion inhibitor
EP2692840A131 Jul 20125 Feb 2014Infineum International LimitedLubricating oil composition
EP2727984A113 Sep 20137 May 2014Infineum International LimitedMarine engine lubrication
EP2735603A116 Oct 201328 May 2014Infineum International LimitedMarine engine lubrication
EP2740782A19 Dic 201311 Jun 2014Infineum International LimitedLubricating oil compositions containing sterically hindered amines as ashless tbn sources
EP2765179A17 Ene 201413 Ago 2014Infineum International LimitedMarine engine lubrication
WO1985003504A2 *18 Ene 198515 Ago 1985Lubrizol CorpProcess for making substituted carboxylic acids and derivatives thereof
WO1987003003A131 Oct 198621 May 1987Lubrizol CorpFuel compositions
WO1994013762A1 *14 Dic 199323 Jun 1994Exxon Chemical Patents IncImproved low sediment process for forming borated dispersant
WO2003095595A17 May 200320 Nov 2003Lubrizol CorpContinuously variable transmission fluids comprising a combination of calcium- and magnesium-overbased detergents
WO2006063161A2 *8 Dic 200515 Jun 2006Lubrizol CorpProcess of preparation of an additive and its use
WO2007008802A2 *11 Jul 200618 Ene 2007Advanced Lubrication TechnologCorrosion prevention and friction reduction coating and low temperature process
WO2008013698A117 Jul 200731 Ene 2008Exxonmobil Res & Eng CoMethod for lubricating heavy duty geared apparatus
WO2008154334A16 Jun 200818 Dic 2008Infineum Int LtdAdditives and lubricating oil compositions containing same
WO2009045979A130 Sep 20089 Abr 2009Lubrizol CorpLubricants that decrease micropitting for industrial gears
WO2009119831A127 Mar 20091 Oct 2009Fujifilm CorporationComposition and method for forming coating film
WO2010077630A18 Dic 20098 Jul 2010The Lubrizol CorporationLubricating composition containing a compound derived from a hydroxy-carboxylic acid
WO2010115594A131 Mar 201014 Oct 2010Infineum International LimitedMarine engine lubrication
WO2011025636A14 Ago 20103 Mar 2011Chemtura CorporationTwo-stage process and system for forming high viscosity polyalphaolefins
WO2011034829A114 Sep 201024 Mar 2011The Lubrizol CorporationLubricating composition containing an ester
WO2011059583A129 Sep 201019 May 2011Chemtura CorporationLubrication and lubricating oil compositions
WO2011066142A117 Nov 20103 Jun 2011The Lubrizol CorporationStabilized blends containing friction modifiers
WO2011066144A117 Nov 20103 Jun 2011The Lubrizol CorporationStabilized blends containing friction modifiers
WO2011066145A117 Nov 20103 Jun 2011The Lubrizol CorporationStabilized blends containing friction modifiers
WO2011130142A111 Abr 201120 Oct 2011The Lubrizol CorporationLow-ash lubricating oils for diesel engines
WO2011149810A123 May 20111 Dic 2011The Lubrizol CorporationLubricating composition
WO2012162020A115 May 201229 Nov 2012The Lubrizol CorporationStabilized blends containing antioxidants
WO2012162027A115 May 201229 Nov 2012The Lubrizol CorporationStabilized blends containing friction modifiers
WO2013003392A127 Jun 20123 Ene 2013Exxonmobil Research And Engineering CompanyMethod of improving pour point of lubricating compositions containing polyalkylene glycol mono ethers
WO2013003394A127 Jun 20123 Ene 2013Exxonmobil Research And Engineering CompanyLubricating compositions containing polyetheramines
WO2013003405A127 Jun 20123 Ene 2013Exxonmobil Research And Engineering CompanyLubricating compositions containing polyalkylene glycol mono ethers
WO2013003406A127 Jun 20123 Ene 2013Exxonmobil Research And Engineering CompanyLow viscosity engine oil with superior engine wear protection
WO2013055480A112 Sep 201218 Abr 2013Exxonmobil Research And Engineering CompanyLow viscosity engine oil compositions
WO2013055481A112 Sep 201218 Abr 2013Exxonmobil Research And Engineering CompanyHigh efficiency engine oil compositions
WO2013055482A112 Sep 201218 Abr 2013Exxonmobil Research And Engineering CompanyLubricating compositions
WO2013066915A131 Oct 201210 May 2013Exxonmobil Research And Engineering CompanyLubricants with improved low-temperature fuel economy
WO2013074498A113 Nov 201223 May 2013Exxonmobil Research And Engineering CompanyMethod for improving engine fuel efficiency
WO2013090051A14 Dic 201220 Jun 2013Chemtura CorporationCross products and co-oligomers of phenylenediamines and aromatic amines as antioxidants for lubricants
WO2013096532A120 Dic 201227 Jun 2013Exxonmobil Research And Engineering CompanyMethod for improving engine fuel efficiency
WO2013101882A127 Dic 20124 Jul 2013The Lubrizol CorporationLimited slip friction modifiers for differentials
WO2013123102A214 Feb 201322 Ago 2013The Lubrizol CorporationLubricating composition including esterified copolymer and low dispersant levels suitable for driveline applications
WO2013123160A114 Feb 201322 Ago 2013The Lubrizol CorporationMixtures of olefin-ester copolymer with polyolefin as viscosity modifier
WO2013151911A11 Abr 201310 Oct 2013The Lubrizol CorporationBearing lubricants for pulverizing equipment
WO2013181318A130 May 20135 Dic 2013Exxonmobil Research And Engineering CompanyLubricant compostions and processes for preparing same
WO2014008121A128 Jun 20139 Ene 2014Exxonmobil Research And Engineering CompanyEnhanced durability performance of lubricants using functionalized metal phosphate nanoplatelets
WO2014047017A117 Sep 201327 Mar 2014The Lubrizol CorporationLubricant comprising a mixture of an olefin-ester copolymer with an ethylene alpha-olefin copolymer
WO2014066444A123 Oct 20131 May 2014Exxonmobil Research And Engineering ComapnyFunctionalized polymers and oligomers as corrosion inhibitors and antiwear additives