US3018173A

US3018173A - Stabilization of hydrocarbons

Info

Publication number: US3018173A
Application number: US655199A
Authority: US
Inventors: Henry A Cyba
Original assignee: Universal Oil Products Co
Current assignee: Universal Oil Products Co
Priority date: 1957-04-26
Filing date: 1957-04-26
Publication date: 1962-01-23
Anticipated expiration: 1979-01-23

Description

3,l8,l'i3 Patented Jan. 23, 1962 ice 18,173 STABILIZATION (ll HYDROCARBUNS Henry A. Cyba, Chicago, L, assignor, by mesne assignments, to Universal Oil Products Company, Des Plaines, Ill., a corporation of Delaware No Drawing. Filed Apr. 26, 1957, Ser. No. 655,199 8 Claims. (Cl. 44-71) This invention relates to the stabilization of organic compounds and more particularly to a novel process for preventing deterioration of organic compounds in storage, during transportation or in use.

The present invention is particularly advantageous for use in the stabilization of hydrocarbon distillates and serves to improve the hydrocarbon distillate in a number of different ways. For example, in fuel oils, burner oils, range oils, diesel oils, marine oils, turbine oils, cutting oils, rolling oils, soluble oils, drawing oils, slushing oils, slushing greases, lubricating oils, lubricating greases, fingerprint removers; etc., the distillate or grease is improved in one or more ways including retarding and/or preventing sediment formation, dispersion of sediment when formed, preventing and/or retarding discoloration, oxidation inhibitor, rust or corrosion inhibitor, detergent, etc. In lubricating type oils, in addition to all or some of the properties hereinbefore set forth, the additive may function as a pour point depressant, viscosity index improver, anti-foaming agent, etc. In liquefied petroleum gases, gasoline, naphtha, aromatic solvents, kerosene, jet fuels, etc., the additive serves as a corrosion inhibitor along with one or more of the other functions mentioned above. In other organic compounds, including alcohols, ethers, chlorinated hydrocarbons, etc., and compositions containing them, glyceridic oils and fats, waxes, other oils and fats of animal or vegetable origin, etc., the additive functions as a beneficent in one or more of the manners herein set forth or otherwise.

The invention is particularly applicable to the stabilization of hydrocarbon distillates heavier than gasoline. The hydrocarbon distillate may be cracked, straight run or mixtures thereof. Many fuel oils and particularly blends of straight run and cracked fuel oils undergo deterioration in storage, resulting in the formation of sediment, discoloration, etc. The formation of sediment is objectionable because the sediment tends to plug burner tips, injectors, etc. In jet fuels, oil-fuel heat exchangers and burner nozzles are plugged, particularly in view of the high temperatures encountered in such service. In dies-e1 fuel, the deterioration tendsto form varnish and sludge in the diesel engine. Discoloration of fuel oils is objectionable for various reasons, including customers preference for light colored oils.

In handling of hydrocarbon distillates and other organic liquids, it is often necessary to transport and/ or store such materials in metal containers, as in steel or other metal pipe lines, drums, tanks, etc. Since these materials often contain varying amounts of water in solution or in suspension which may separate, due to temperature changes, internal corrosion of the container by separating water almost invariably occurs to a greater or lesser degree. The water thus separated forms as a film or in minute droplets in the pipe line or on the container walls or even in small pools at the bottom of the container. This brings about ideal conditions for corrosion and consequent damage to the metal surfaces of the container, as well as the serious contamination of the hydrocarbon oil or other materials contained therein by the corrosion products.

Corrosion problems also occur, for example, in the lubrication of internal combustion engines or steam engines, including turbines and other similar machinery, in which a quantity of water often is observed as a separate phase within the lubricating system as a result of the condensation of water from the atmosphere or, in the ease of internal combustion engines, as the result of dispersion or absorption in lubricating oil of water formed as a product of fuel combustion. Water in such instances oor-rodes the various metal parts of the machinery with which it comes into contact, the corrosion products causing further mechanical damage to bearing surfaces and the like due to their abrasive nature and catalytically promoting the chemical degradation of the lubricant. Corrosion problems also arise in the preparation, transportation and use of various coating compositions such as greases, household oils, paints, lacquer, etc., which often are applied to metal surfaces for protective purposes.

In one embodiment, the present invention relates to a process for stabilizing an organic substrate against deterioration which comprises incorporating therein a stabilizing concentration of the reductive alkylation product of a ketone containing at least eight carbon atoms and an aminoalkyl alkanolamine of the following general formula:

where n is from 2 to 4 and R is selected from the group consisting of hydrogen, a hydrocarbon group, and mixtures thereof.

In a specific embodiment, the present invention relates to the stabilization of burner oil which comprises incorporating therein a stabilizing concentration of the reductive alkylation product of diheptadecyl ketone and aminoethyl ethanolamine.

In another embodiment, the present invention relates to the stabilization of an organic substrate against deterioration which comprises incorporating therein a stabilizing concentration of the additive prepared by the reductive alkylation of a ketone with at least eight carbon atoms and an aminoalkyl alkanolamine of the structure herein described and the further reaction of the reductive alkylation product with a dicarboxylic acid or anhydride.

In another embodiment, the present invention relates to an organic substrate and particularly hydrocarbon oil heavier than gasoline subject to deterioration containing a stabilizing concentration of an additive herein set forth.

In still another embodiment, these reductive alkylation products and their further reaction products are new compositions of matter and are so being claimed in the present application.

In addition to the particular utility as additives to organic compounds, the products of the present invention and particularly the reaction product of the reductive alkylation product with dibasic acid or anhydride will have utility as cross-linking agents for resins, plastics and elastomers, and as intermediates for the preparation of polyurethanes. Polyfunctional chain-extending or network-extending agents are generally employed to create structures of high molecular weight in the preparation of resins, plastics and elastomers. Accordingly, polyethers, polyamides, polyurethanes and epoxy resins, which contain functional groups including, for example, hydroxyl, carboxyl, isocyanato or epoxy groups, which are free to react with functional groups of the reaction products of the present invention, are converted into polymeric structures.

The additive for use in the present invention is prepared by the reductive alkylation of a ketone containing at least eight carbon atoms and certain aminoalkyl alkanolamines. It is essential that the ketone contains at least eight carbon atoms and preferably at least twelve carbon atoms, and it usually will contain from about eight and preferably from about twelve to about forty carbon atoms, although in some cases, ketones containing up to about fifty carbon atoms may be employed.

The preferred ketone for use in the present invention comprises an aliphatic ketone. Any suitable aliphatic ketone may be employed. Preferred illustrative ketones include methyl decyl ketone, methyl undecyl ketone,

methyl dodecyl ketone, methyl tridecl ketone, methyl tetradecyl ketone, methyl pentadecyl ketone, methyl hexadecyl ketone, methyl heptadecyl ketone, methyl octadecyl ketone, methyl nonadecyl ketone, methyl eicosyl ketone, methyl heneicosyl ketone, methyl docosyl ketone, methyl tricosyl ketone, methyl tetracosyl ketone, methyl pentacosyl ketone, methyl hexacosyl ketone, methyl heptacosyl ketone, methyl octacosyl ketone, methyl nonacosyl ketone, methyl triacontyl ketone, methyl hentriacontyl ketone, methyl dotriacontyl ketone, methyl tritriacontyl ketone, methyl tetratriacontyl ketone, methylpentatriacontyl ketone, methyl hexatriacontyl ketone, methyl octatriacontyl ketone, etc., ethyl nonyl ketone, ethyl decyl ketone, ethyl undecyl ketone, ethyl dodecyl ketone, ethyl tridecyl ketone, ethyl tetradecyl ketone, ethyl pentadecyl ketone, ethyl hexadecyl ketone, ethyl heptadecyl ketone, ethyl octadecyl ketone, ethyl nona-. decyl ketone, ethyl eisocyl ketone, ethyl heneicosyl ketone, ethyl docosyl ketone, ethyl tricosyl ketone, ethyl tetracosyl ketone, ethyl pentacosyl ketone, ethyl hexacosyl ketone, ethyl heptacosyl ketone, ethyl octacosyl ketone, ethyl nonacosyl ketone, ethyl triacontyl ketone, ethyl hentriacontyl ketone, ethyl dotriacontyl ketone, ethyl tritriacontyl ketone, ethyl tetratriacontyl ketone, ethyl pentatriacontyl ketone, ethyl hexatriacontyl' ketone, ethyl heptatriacontyl ketone, etc., propyl octyl ketone, propyl nonyl ketone, propyl decyl ketone, propyl undecyl ketone, propyl dodecyl ketone, propyl tridecyl ketone, propyl tetradecyl ketone, propyl pentadecyl ketone, propyl hexadecyl ketone, propyl heptadecyl ketone, propyl octadecyl ketone, propyl nonadecyl ketone, propyleicosyl ketone, propyl heneicosyl ketone, .propyl docosyl ketone, propyl tricosyl ketone, propyl tetracosyl ketone, propyl pentacosyl ketone, propyl hexacosyl ketone, propyl heptacosyl ketone, propyl octacosyl ketone, propyl nohacosyl ketone, propyl triacontyl ketone, propyl hentriacontyl ketone, propyl dotriacontyl ketone, propyl tritriacontyl ketone, propyl tetratriacontyl ketone, propyl pentatriacontyl ketone, propyl hexatriacontyl ketone, etc., butylheptyl-ketone, butyl octyl ketone, butylnonyl' ketone,- butyl decyl ketone, butyl undecyl.ketone,,but'yl dodecyl ketone, butyl tridecyl ketone, butyl tetradecyl ketone, butyl pentadecyl ketone, butyl hexadecyl ketone, butyl heptadecyl ketone, butyl octadecyl ketone, butyl nonadecyl ketone, butyl eicosyl ketone, butyl heneicosyl ketone, butyl docosyl ketone, butyl tricosyl ketone, butyl tetracosyl ketone, butyl pentacosyl ketone, butyl'hexacosyl ketone, butyl heptacosyl ketone, butyl octacosyl ketone, butyl nonacosyl ketone, butyl triacontyl ketone, butyl hentriacontyl ketone, butyl dotriacontyl ketone, butyl tritriacontyl ketone, butyl tetratriacontyl ketone, butyl pentatriacontyl ketone, etc.

The specific ketones listed above comprise those containing from 12 to 40 carbon atoms each. It is understood that ketones containing from 8 to 12 carbon atoms may be employed, as well as symmetrical ketones, that is, containing the same number of carbon atoms attached to the ketone carbon atom as, for example, dihexyl ketone, dioctyl ketone, didodecyl ketone, diheptadecyl ketone, etc., or ketones containing one more carbon atom in one group attached to the keto carbon atom than in the other group as, for example, heptyl octyl ketone, decyl undecyl ketone, heptadecyl octadecyl ketone, etc.

A number of ketones containing at least 12 carbon atoms are available as mixtures which are either products orby-products of commercial operations. These mixtures generally are available at comparatively low cost and, as another advantage of the present invention, the mixtures may be used Without the added time and expenseof separating specific compounds in pure state. ture available commercially as a primary product of the process is Stearone which is diheptadecyl ketone.

One such mix-' While the alkyl ketones are preferred, in some cases, ketones containing unsaturation in the aliphatic group may be employed. Also, aromatic ketones or aromatic aliphatic ketones may be utilized in some cases. Furthermore, While it generally is preferred to utilize the same lcetonein forming the reductive alkylation product, it is understood, in some cases, that a mixture of ketones may be employed, at least one and preferably all of the ketones containing at least 8 and still more preferably at least 12 carbon atoms each. In some cases, the ketone may contain a non-hydrocarbon substituent in the chain, this substituent containing oxygen, nitrogen, sulfur, etc.

From the above, it will be noted that a number of different ketones meeting the requirements hereinbefore set forth may be employed. However, it is understood that the different ketones are not necessarily equivalent for use in preparing the reductive alkylation product and that the particular ketone' will be selected with regard to the particular aminoalkyl alkanolamine with which it is to be reacted, the particular substrate in which the additive is to be used, availability, cost, etc.

The aminoalkyl alkanolamine to be utilized for reductive alkylation with the hereinbefore described ketone is. illustrated by the following general formula:

HzN(CHR)nl T (CHR)nOH where n is from 2 to 4 and R is selected from the group consisting of hydrogen, a hydrocarbon group and mixtures thereof.

Where R in the above general formula is hydrogen, illustrative compounds include aminoethyl ethanolamine, aminopropyl propanolamine, aminobutyl butanolamine, arninopropyl ethanolamine, aminobutyl ethanolamine, aminoethyl propanolamine, aminobutyl propanolamine, aminoethyl butanolamine and aminoprop-yl butanolamine. In general, it is preferred that both R substitutents are the same. A particularly preferred compound for use in the present invention comprises aminoethyl ethanolamine.

Where R in the above general formula is a hydrocarbon group, the hydrocarbon group is selected from alkyl, alkaryl, aryl, aralkyl, cyclohexylalkyl, cyclohexyl, alkyl cyclohexyl, etc. In another embodiment, the hydrocarbon group is selected from alkenyl, alkenyl aryl, aryl alkenyl, alkenyl cyclohexyl, cyclohexyl alkenyl, cyclopentenyl, etc. In all cases, it will be noted that there are from 2 to 4 carbon atoms between the nitrogen atom and the hydroxyl group. Where R is selected from a mixture of hydrogen and alkyl groups, illustrative compounds include l-aminoethylaminopropanol-2, l-aminoethylamino-butanol-2, 1-aminoethylamino-pentanol-Z, l-aminoethylamino-hexan0l-2, l-aminoethylamino-heptanol-Z, 1-aminoethylamino-octanol-Z, etc., l-aminoethylamino-but anol-3, 1-aminoethylarnino-pentanol-3, 1-aminoethylamino-hexanol-3, l-aminoethylamino-heptanol-3, 1-aminoethylamino-octanol-3, etc., 1-aminoethylamino-pentanol-4, 1-aminoethylamino-hex-anol-4, 1-aminoethylamino-heptanol-4, 1-aminoethylamino-octanol-4, etc., 1-aminopropylamino-propanol-2, 1-aminopropylamino-butanol-Z, 1-am:inopropylamino-pentanol-Z, 1-aminopropylamino-butanol2, 1-aminopropylamino-pentanol2, l-aminopropylamino-hexanol-Z, 1-aminopropylamino-heptanol-2, l-aminop-ropylamino-octanol-Z, etc., l-ar1inopropylamino-butanol-3, l-aminopropylamino-pentanol-3,

1-arninopropylamino-hexanol-3, 1-a minopropylamino-heptanol-3, 1-aminopropylamino-octanol-3, etc., 1-a.rninoethylamino-pentanol-4, 1-aminopropylamino-hexanolt, 1-aminopropylamino-heptanol-4, 1-aminopropylarnino-octanol-4, etc., l-aminobutylamino-propanol-Z, 1-aminobutylamino-butanol-2, l-aminobutylamino-pentanol-Z, 1-aminobutylam-ino-hexanol-Z, 1-aminobutylarnino-heptanol-2, 1-aminobutylamino-octanol-2, etc., 1-aminobutylamino-butanol-3, 1-aminobutylamino-pentanol-3, 1-aminobutylamino-hexanol-3, 1-aminobuty lamino-heptanol-3, 1-aminobutylamino-octanol-3, etc., 1-aminobutylamino-pentanol-4, 1-aminobutylamino-hexanoll, 1 aminobutylamino-hepanol-4, 1-aminoethylamino-octanol-4, etc.

Where R is an aryl group, illustrative compounds include 1-aminoethylamino-Z-phenyl-ethanol-Z, l-arninoethylamino-2-tolyl-propanol-3, l-aminoethylamino-2-phenyl-butanol-4, 1-arninoethylamino-2-tolyl-hexanol-2, 1-aminoethylamino-Z-phenyl-heptanol-3 1-aminoethylamino-2-tolyl-octanol-4, l-amir1opropylamino-2-phenyl-ethanol-2, 1-aminopropylamino-Z-tolyl-propanol-3, etc.

It will be noted that a number of different aminoalkyl 'alkanolamines may be utilized in preparing the reductive alkylation products. It is understood that the different compounds which may be used are not necessarily equivalent and that the particular compound will be selected with regard to the ketone with which it is to be reacted, as well as the particular substrate in which the additive is to be used, availability, cost, etc.

The reductive alkylation of the ketone and aminoalkyl alkanolamine may be effected in any suitable manner. In general, the reaction is effected using an equimolar proportion of ketone and aminoalkyl alkanolamine, although an excess of one or the other may be employed in order to insure complete reaction.

In a preferred embodiment, the reductive alkylation is efiected in two steps. In the first step, a Schifis base of the ketone and aminoalkyl alkanolarnine is prepared, and the Schiffs base then is reduced to the desired product. In the first step, the ketone and aminoalkyl alkanolarnine are reacted by heating at refluxing conditions. For ease in handling and operation, a solvent preferably is employed. Any suitable solvent may be used and preferably comprises a hydrocarbon including benzene, toluene, xylene, ethylbenzene, cumene, Decalin, naphtha, etc. The temperature of reaction will depend upon whether a solvent is employed and, when employed, upon the particular solvent. In general, the temperature of reaction will be within the range of from about 80 to about 200 C. Water formed during the reaction may be removed in any suitable manner including, for example, by separating under reduced pressure, by removing an azeotrope of water-solvent, by distilling the reaction product at elevated temperature, etc.

The Schifis base formed in the first step is subjected to reduction in any suitable manner. Preferably this is effected in the presence of hydrogen and a hydrogenation catalyst. Any suitable catalyst may be employed including nickel, platinum, palladium, etc., preferably composited with a suitable support. A particularly preferred catalyst comprises a composite of platinum and alumina, which may or may not contain combined halogen. The platinum generally is present in the catalyst in a concentration of from about 0.1 to about 2% by weight of the final catalyst and the halogen, when present, is in a concentration of total halogen of from about 0.01% to about 1% by weight of the final catalyst, the halogen preferably comprising fluorine and/ or chlorine. A preferred nickel catalyst is a composite of nickel and kiesclguhr containing from about 30 to about 60% by weight of nickel. It is understood that the platinum or nickel may be present as the free metal and/or compounds thereof. These catalysts are well-known in the art and need not be described in detail in the present application because no novelty is being claimed herein for the catalyst per se. While these are the preferred catalysts, it is understood that any other suitable hydrogenation catalyst may be employed. The temperature of the hydrogenation will depend upon the particular catalyst and method employed, and in general will be within the range of from about to about 300 C., although higher or lower temperatures may be employed in some cases. Generally the hydrogenation is effected using a hydrogen pressure within the range of from about 50 to about 3000 pounds per square inch or more.

In another embodiment, the reductive alkylation is effected in a single step. In this embodiment, the reaction is conducted in the presence of a suitable reductive alkylation catalyst and hydrogen. A preferred catalyst comprises the platinum-containing catalyst hereinbefore described. Other catalysts include a composite of copper oxide, chromium oxide and barium oxide, as well as catalysts containing nickel, palladium, etc. The temperature employed generally will be between about 100 and about 250 C. and the hydrogen pressure generally is from about 100 to about 3000 pounds per square inch.

In another embodiment of the invention, the additive and novel composition of the present invention comprises the reaction product of the reductive alkylation product prepared in the above manner with a polycarboxylic acid or anhydride. The polycarboxylic acid preferably comprises an aliphatic dicarboxylic acid. Illustrative dicarboxylic acids include oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, fumaric, citraconic, mesaconic, etc. While the dicarboxylic acids are preferred, it is understood that polycarboxylic acids containing three, four, or more carboxylic acid groups may be employed. Furthermore, it is understood that a mixture of polycarboxylic acids and particularly of dicarboxylic acids may be used. A number of relatively inexpensive dicarboxylic acids comprising a mixture of these acids are marked commercially under various trade names, including VR-l acid, Dimer acid, etc., and these acids may be used in accordance with the present invention. For example, VR-l acid is a mixture of dicarboxylic acids and has an average molecular weight of about 700, is a liquid at 77 F., has an acid number of about and an iodine number of about 36. It contains 36 carbon atoms per molecule.

Another preferred dicarboxylic acid comprises a mixed acid being marketed commercially under the trade name of Empol 1022. This dimer acid is a dilinoleic acid and is represented by the following general formula:

This acid is a viscous liquid, having an apparent molecular weight of approximately 600. It has an acid value of 180-192, an iodine value of 80-95, a saponification value of -195, a neutralization equivalent of 290-310, a refractive index at 25 C. of 1.4919, a specific gravity at 15.5 C./15.5 C. of 0.95, a flash point of 530 F., a fire point of 600 F., and a viscosity at 100 C. of 100 centistokes.

While the polycarboxylic acid may be employed, advantages appear to be obtained in some cases when using anhydrides thereof and particularly alkenyl-acid anhydrides. A preferred alkenyl-acid anhydride is dodecenylsuccinic anhydride. Other alkenyl-acid anhydrides include butenyl-succinic anhydride, pentenyl-succinic anhydride, hexenyl-succinic anhydride, heptenyl-succinic anhydride, octenyl-succinic anhydride, nonenyl-succinic anhydride, decenyl-succinic anhydride, undecenyl-succinic anhydride, tridecenyl-succinic anhydride, tetradecenylsuccinic anhydride, pentadecenyl-succinic anhydride, hexadecenyl-succinic anhydride, heptadecenyl-succinic anhydride, octadecenyl-succinic anhydride, nonadecenyl-succinic anhydride, eicosenyl-succinic anhydride, etc. While the alkenyl-succinic anhydrides are preferred, it is understood that the alkyl-succinic anhydrides may be employed, the alkyl groups preferably corresponding to the alkenyl groups hereinbefore specifically set forth. Similarly, while the aliphatic succinic anhydrides are preferred, it is understood that the anhydrides and particularly aliphatic-substituted anhydrides of other acids may be employed including, for example, adipic anhydride and particularly aliphatic a-dipic anhydrides, glutaric anhydride and particularly aliphatic glutaric anhydrides, etc.

In another embodiment of the present invention, the reductive alkylation product is reacted 'further with an alpha, beta-unsaturated polycarboxylic acid, anhydride or ester formed by the reaction of a terpene with an alpha,beta-unsaturated polycarboxylic acid, anhydride or ester. The reaction product will comprise primarily the anhydride but the acid and/or ester also will be present. Any suitable terpenic compound may be reacted with any suitable alpha,beta-unsaturated polycarboxylic acid, anhydride or ester to form the reaction product for subsequent condensation with the alkanolamine. In one em 'bodiment, a terpene hydrocarbon-having the formula C H is employed, including alpha-pinene, beta-pinene, dipentene, dlimonene, l-limonene and terpinoline. These terpene hydrocarbons have boiling points ranging from about 150 to about 185 C. In another embodiment the terpene may contain three double bonds in monomeric form, including terpenes as allo-o-cymene, o-cymene, myrcene, etc. Other terpenic compounds include alphaterpinene, p-cyrnene, etc. Also included as terpenic compounds are rosins comprising the terpenic hydrocarbons and/ or terpenic acids. These rosins and acids generally are tricyclic compounds. However, they are obtained from pine trees and therefore may be included in' the broad classification as terpene or terpenic compounds.

As hereinbefore set forth, the terpene is reacted with an alpha,beta-unsaturated polycarboxylic acid, anhydride or ester thereof. Any unsaturated polycarboxylic acid having a point of unsaturation between the alpha and beta carbon atoms may be employed. Illustrative unsaturated dicarboxylic acids include maleic acid, fumaraic acid, citraconic acid, mesaconic acid, aconitic acid, itaconic acid. While the diarboxylic acids are preferred, it is understood that alpha, beta-unsaturated polycarboxylic acids containing three, four or more carboxylic acid groups may be employed. Furthermore, it is understood that amixture of alpha,beta-unsaturated polycarboxylic acids and particularly of alpha,beta-unsaturated dicarboxylic acids may be used.

While the alpha,beta-unsaturated polycarboxylic acid may be employed for reaction with the terpene, advantages appear to be obtained in some cases when using the anhydrides thereof. lllustrative anhydrides include maleic anhydride, citraconic anhydride, aconitic anhydride, itaconic anhydride, etc. It i understoodv that a mixture of anhydrides may be employedand also that the anhydride may contain substituents and particularly hydrocarbon groups attached thereto. Furthermore, it is understood that the various anhydrides are not necessarily equivalent. Also, it is understood that esters of the alpha,beta-unsaturated polycarboxylic acids may be employed, the ester group being selected from alkyl, alltaryl, aralkyl, aryland cycloalkyl substituents replacing one or more of the hydrogen atoms of the carboxylic acid groups.

The reaction of terpene and alpha,beta-unsaturated acid. anhydride or ester generally is effected at a temperature of from about 150 to about 300 C., and preferably of from about 160 to about 200 C. The time of heating will depend upon the particular reactants and may range from 2 hours to 24 hours or more. When desired, a suitable solvent may be utilized. Following the reaction, impurities or unreacted materials may be removed by vacuum distillation or otherwise, to leave a resinous product which may be a viscous liquid or a solid.

A terpene-maleic anhydride reaction product is available commercially under the trade name of Petrex acid. This acid is a stringy, yellow-amber colored mass and is mostly dibasic. It has an acid number of approximately 530, a molecular weight of approximately 215 and a softening point of 40-50 C.

Another reaction product is available commercially under the trade name of Lewiso-l 40 acid. This is a tricarboxylic acid and is formed by the reaction of fu maric acid and rosin. It is a hard, brittle solid having a softening point of l50160 C. and a specific gravity at 25/25 C. of 1.178.

The reaction of the reductive alkylation product with the dicarboxylic acid, anhydride or the terpene reaction product is effected in any suitable manner. In general, the reaction is effected using one or tWo mols of the reductive alkylation product per one mol of acid, anhydride or terpene reaction product, although an excess of one of the reactants may be employed in order to insure complete reaction. The reaction generally is eifected at a temperature above about 8 0 C. and preferably at a higher temperature which usually will not exceed about 200 C., although higher or lower temperatures may be employed in some cases. The exact temperature will depend upon whether a solvent is used and, when employed, on the particular solvent. For example, with benzene as the solvent, the temperature will be in the order of C., with toluene the temperature will be in the order of C. and with xylene in the order of l50155 C. Other preferred solvents include cumene, naphtha, decalin, etc. Any suitable amount of the solvent may be employed but preferably should not comprise a large excess because this will tend to lower the reaction temperature and slow the reaction. Water formed during the reaction may be removed in any suitable manner including, for example, by operating under reduced pressure, by removing an azeotrope of Water-solvent, by distilling the reaction product at an elevated temperature, etc. A higher temperature may be utilized in effecting the reaction in order to remove the water as it is being formed. However, for many uses, the reaction need not go to completion, but in any event at least a substantial portion of the reaction product will comprise that formed by the condensation of the reductive alkylation product with the terpene-acid, anhydride or ester reaction product.

Here again, it is understood that a number of different compounds may be prepared and used in accordance with the present invention and will depend upon the specific reductive alkylation product and dicarboxylic acid, anhydride or terpene reaction product employed. It is understood that the different compositions are not necessarily equivalent in the same or different substrates or for the same or different uses.

The reductive alkylation product or further reaction product thereof, as hereinbefore described, is recovered as a final product ranging from a clear liquid to a viscous liquid or solid. In some cases, the product will be marketed and utilized as a solution in a solvent. Conveniently, this solvent comprises the same solvent used in preparing the reductive alkylation product and/or further reaction product and is recovered in admixture with oil and evaluated in the Erdco test.

at least a portion of the solvent, thereby avoiding the necessity of removing all of the solvent and subsequently adding it back. When a more dilute solution is desired than is recovered in the manner hereinbefore set forth, it is understood that the same or different solvent may be commingled with the mixture to form a solution of the desired concentration.

The concentration of additive to be usedin the organic substrate will depend upon the particular substrate and the particular benefits desired. In general, the additive will be used in a concentration of from about 0.00001% to about by weight or more and more specifically is sued in a concentration of from about 0.0001% to about 1% by weight of the substrate. The additive may be used along with other additives which are incorporated in the substrate for specific purposes including, for example, metal deactivators, antioxidants, antiozidants, synergists, dyes, fuel improvers, etc.

The additive may be incorporated in the substrate in any suitable manner. As hereinbefore set forth, the additive conveniently is marketed and utilized as a solution in a suitable solvent, including hydrocarbons and particularly aromatic hydrocarbons as benzene, toluene, xylene, cumene, etc. When the additive is to be incorporated in a liquid substrate, it may be added thereto in the desired amount and the resultant mixture suitably agitated in order to obtain intimate admixing of the additive in the substrate. When the additive is to be utilized as a corrosion inhibitor in plant equipment, it may be introduced into a fractionator, vapor line or at any other suitable point in order to prevent corrosion of the plant equipment. In this embodiment, the additive carries over into the product of the process and also serves therein as a beneficent. It is understood that a portion of the additive may be introduced into the plant equipment and an additional portion of the additive incorporated in the effluent product when so desired.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

EXAMPLE I The additive of this example was prepared by the reductive alkylation of stearone and aminoethyl ethanolamine. As hereinbefore set forth, stearone is diheptadecyl lietone. The reductive alkylation was prepared in two steps as follows: 538 grams (one mol) of stearone and 109 grams (one mol+5% excess) of aminoethyl ethanolamine were refluxed in 100 grams of toluene. 18.6 cc. of water was recovered from the reaction. The resultant Schiifs base was reduced in a rocker bomb at 140 C. with 125 atmospheres of hydrogen in the presence of 100 grams of a catalyst comprising alumina, about 0.4% platinum and about 0.3% combined halogen. The hydrogenated product was dissolved in benzene, filtered to remove catalyst, and the benzene and toluene were removed by evaporation in a steam bath under water pump vacuum. The product is a waxy-white solid having a basic mol combining weight of 329. The calculated basic rnol combining weight is 312.

The reductive alkylation product prepared in the above manner was evaluated in a method referred to as the Erdco test. In this method, heated oil is passed through a filter, and the time required to develop a diiferential pressure across the filter of 25 in. Hg is determined. It is apparent that the longer the time, the more effective is the additive. However, with a very effective additive, the time to reach a differential pressure across the filter of 25 in. Hg is lengthened beyond reasonable limits that the test is stopped after about 300 minutes and the differential pressure after that time is reported.

0.001% of the reductive alkylated product prepared in the above manner was incorporated in a commercial range After 300 minutes, the difierential pressure across the filter was 0.2 in. Hg.

On the other hand, a control sample (not containing this additive) developed a differential pressure across the filter of 25 in. Hg in about 125 minutes.

In still another test, 0.0005 by weight of the same additive in another sample of the range oil gave a differential pressure across the filter of 0.4 in. Hg after 300 minutes.

From the above data, it will be noted that the additive of the present invention served to considerably retard deterioration of the range oil and thus will prevent clogging of burner tips, injectors, etc., during use ofthe oil as fuel oil, diesel fuel, jet fuel, etc. It is interesting to note that the additive was very effective even at the very low range of 0.0005% by weight.

EXAMPLE II The additive of this example was prepared by the twostep reductive alkylation of methyl heptadecyl ketone and aminoethyl ethanolamine. 282 grams (one mol) of methyl heptadecyl ketone and 109 grams (one mol) of aminoethyl ethanolamine and grams of xylene were refluxed,

with the evolution of 22 cc. of water. The resultant Schiifs base with 200 grams of toluene was reduced in the presence of 100 grams of alumina-platinum-combined halogen catalyst referred to in Example I at C.

using atmospheres of hydrogen. The product was dissolved in benzene and filtered. The toluene and benzene were removed on a steam bath at water pump vacuum. The resulting product is an amber, greasy solid, having a basic mol combining weight of 201. Calculated combining weight is 185. For additional characterization, the product was distilled at a vacuum of 0.35 mm. Hg. The main fraction (about 80-90% of the total) distilled at 212214 C. This distillate had a basic mol combining weight of 187.5 and a molecular weight of 375 (theoretical is 370). It is a soft pale-orange microcrystalline waxy solid. Its specific gravity at 60 F. is 0.8849.

0.001% by weight of the total reductive alkylated product prepared in the above manner was incorporated in another sample of the range oil described in Example I and evaluated in the Erdco test. After 300 minutes, the differential pressure across the filter was 1.4 in. Hg. In another run using 0.0005% by weight of the additive, the differential pressure across the filter after 300 minutes was 2.3. Here again, it will be noted that the additive of the present invention served to retard deterioration of the range oil.

EXAMPLE III As hereinbefore set forth, the reductive alkylation product may be further reacted with a terpene reaction product. In this example, the reductive alkylation product of Example I was reacted with Petrex acid, the latter being described in detail hereinbefore. 131.6 grams (0.4 equivalent) of the reductive alkylation product of Example I and 21 grams (0.2 equivalent) of Petrex acid were dissolved in 100 grams of xylene and refluxed. 2.3 cc. of water was collected after 24 hours of refluxing. The solvent was removed on a steam bath at water pump vacuum.

0.001% by weight of the reaction product prepared in the above manner was incorporated in another sample of the range oil described in Example I and, when evaluated in the Erdco test, gave 0.9 in. Hg after 300 minutes.

EXAMPLE IV The additive of this example was prepared by the twostep reductive alkylation of methylhexyl ketone and aminoethyl ethanolamine. The reductive alkylation was effected in substantially the same manner as hereinbefore set forth. 520 grams (4.06 mols) of methylhexyl ketone was refluxed with 208 grams (two mols) of aminoethyl ethanolamine. The reduction of the Schitfs base was effected at C. in the presence of 100 atmospheres of hydrogen in a rocker bomb for six hours using catalyst previously described. In this case, an excess of ketone was employed, and the excess ketone was removed by distillation. The final product was a water-white liquid, distilling at l724 C. and had a basic mol combining weight of 119.2. The calculated mol combining Weight is 108. Other physical properties are a specific gravity of 60 F. of 0.8984 and an index of refraction at 20 C. of 1.4630.

0.01% by weight of the reductive alkylation product was evaluated in the Erdco test in another sample of the range oil and gave 2.3 in. Hg after 180 minutes.

of the same additive (one gram) was mixed together with commercial epoxy resin Epon 828. The mixture was cured at 170:2" C. for 1% hours. After this time, the Epon 828 was cured to a somewhat soft mass. The example indicates that the alkylation product of aminoethyl ethanolamine with methylhexyl ketone acts .as curing agent for epoxy resins.

EXAMPLE V Another method of evaluating the additives is by a test known as recycle test in which successive 400 cc. portions of a commercial fuel oil is passed through a 400 mesh screen, and the time in seconds for each successive portion to pass through the screen is measured. It is apparent that the time required for the successive portions to pass through the screen is an indication of deterioration of the oil, the longer time indicating greater deterioration. The following table reports results obtained when using a control sample (not containing the :additive) and when using two different preparations of the present invention, the additives beig used in a con- :centration of 0.01% by weight of the oil. Additive I is the additive described in Example I. Additive II is :the additive described in Example III.

Another indication of deterioration is in discoloration and the following table also reports the colors of the different samples of the oil after storage at 100 F. for about 180 days. The colors were determined in a Lumetron, model 402-E, spectrophotometer. Distilled water has a rating of 100 and very dark oil has a rating of 0.

Table 1 [Time in seconds for successive 400 cc. portions to pass] Additive 1 l 2 3 Color EXAMPLE v1 As hereinbefore set forth, the additive of the present invention also may serve as a corrosion inhibitor. This was evaluated in an apparatus designed to simulate plant usage. In this apparatus, a highly polished steel strip is suspended in a neck of a flask containing 300 cc. of a hexane fraction and 25 cc. of water, to which ammonium chloride and hydrochloric acid is incorporated to give a pH of about 1.65. The flask is heated to a temperature of about 100 C. and hydrogen sulfide is continuously passed over the steel strip for 10 hours. At the end of this time, the steel strip is removed for visual observation and determination of the weight lost.

Another portion of the additive prepared in accordance with Example I was evaluated by this method. The results of a control sample not containing this additive and.

samples containing different concentrations of the additive are shown in the following table:

From the data in the above example, it will be seen that the additive of the present invention effectively reduced corrosion.

EXAMPLE VII The composition of this example was prepared by the two-step reductive alkylation of methyl pentadecyl ketone and aminoethyl ethanolamine. 508 grams (two mols) of methyl pentadecyl ketone were refluxed with 218 grams (two mols+ 10 grams excess) of aminoethyl ethanolamine. The Schiffs base was reduced at 160 C. and atmospheres of hydrogen for six hours in the presence of 100 grams of the alumina-platinum-combined halogen catalyst previously described. The reduced product was then heated at C. under 0.3 mm. vacuum to remove excess aminoethyl ethanolamine. The product was a yellow-green liquid at room temperature. The mol combining weight was 180, calculated combining weight is 171. The molecular weight was 360. The theoretical molecular weight is 341. For the purpose of further characterization, the product was distilled at a vacuum of 0.3 mm. Hg. The main fraction, about 90% of the total, had a boiling point of 20l203 C. This is a pale-tan, almost white 'liquid, solidifying or melting at about 22- 24 C. The liquid solidifies in the form of fine soft needles. Titrated with 0.1 normal perchloric acid, it gave a basic mol combining weight of 177.3 or a molecular weight of 354.6. The specific gravity of the product at 60 F. is 0.8855. The index of refraction at 20 C. is 1.5280.

EXAMPLE VIII Jet fuels in supersonic military aircraft under the effect of high temperatures oxidize while being used as cooling mediums in heat exchangers with temperatures ranging to 500 F. or higher. The fuel degradation products formed either in heat exchangers or in burner nozzles foul the operation of the engine. The formation of the deposit is prevented by a reaction product of Petrex acid and a reductive alkylation product of stearone and aminoethyl ethanolamine described in Example I. In this condensation, 21 grams of Petrex acid (0.2 equivalent) was reacted with 65.8 grams (0.2 equivalent) of the reductive alkylation product of stearone and aminoethyl ethanolamine, described inExample I, in 100 grams of xylene. After 24 hours refluxing, the xylene was removed on a steam bath under vacuum. The resulting product is a polyamine having a basic mol combining weight of 928 and an acidic mol combining weight of 5550 (acid number 10.1).

0.001% of this condensation product was incorporated in another range oil containing 15% of catalytically cracked gasoline, and was evaluated in the Erdco test. After 180 minutes, the differential pressure across the filter was 0.1 in. Hg. The filter temperature was kept at 400 F. and the preheater temperature at 350 F. No visible deposit was formed on the preheater tube after 180 minutes operation. The non-inhibited fuel reached a mercury dilferential of 25 inches after 25 minutes. The absence of any deposit on the preheater tube indicates that the additive is effective as a heat exchanger antifouling agent at high temperature.

13 EXAMPLE IX 65.8 grams of the reductive alkylation product of stearone and aminoethyl ethanolamine was reacted with 27.5 grams of dodecenyl succinic anhydride in 200 grams of xylene. Two cc. of water was collected in a Dean-Stark water trap. The xylene was removed on a steam bath under vacuum. The product is a polymer having a basic equivalent weight of 749.

EXAMPLE X 54 grams (0.15 mol) of the reductive alkylation prodnet of methyl pentadecyl ketone and aminoethyl ethanolamine (Example VII) was refluxed with 31.2 grams of Petrex acid (0.15 mol equivalent) in 100 grams of xylene. 2.6 cc. H O was collected after nine hours refluxing, The xylene was removed under vacuum. The resulting polymer is a somewhat rubbery soft solid. The isocyanate equivalent is 203, basic equivalent of 559 and acidic equivalent of 1035.

EXAMPLE XI 54.0 grams of the reductive alkylation product described in Example VII, equivalent to 0.15 mol, was reacted with 41.25 grams of dodecenyl succinic anhydride (equivalent to 0.15 mol) in 200 grams of xylene. After 12 hours of refluxing, 2.6 cc. water was collected. The Xylene was removed under vacuum at 160 C. The resulting polymer is a heavy almost solid mass. The average cryoscopic molecular weight is 1859, isocyanate equivalent is 320, basic equivalent is 715 and acidic equivalent is 1930.

I claim as my invention:

1. A hydrocarbon distillate normally tending to deteriorate containing a stabilizing concentration of an inhibitor comprising the product resulting from the reductive alkylation at a temperature of from about 80 to about 300 C. of an equimolar proportion of a ketone containing from 8 to about 40 carbon atoms and an aminoalkylalkanolamine of the following general formula Where n is from 2 to 4 and R is Selected from the group consisting of hydrogen and an alkyl group of from 1 to 8 carbon atoms,

2. A hydrocarbon distillate normally tending to deteriorate containing a stabilizing concentration of an inhibitor comprising the product resulting from the reductive alkylation at a temperature of from about 80 to about 300 C. of an equimolar proportion of a dialiphatic ketone containing from 12 to about 40 carbon atoms and an aminoalkyl alkanolamine of the following general formula where n is from 2 to 4 and R is selected from the group consisting of hydrogen and an alkyl group of from 1 to 8 carbon atoms.

3. Burner oil normally tending to deteriorate containing a stabilizing concentration of an inhibitor comprising the product resulting from the reductive alkylation at a temperature of from about 80 to about 300 C. of an equimolar proportion of diheptadecyl ketone and aminoethyl ethanolamine.

4. Burner oil normally tending to deteriorate containing a stabilizing concentration of an inhibitor comprising the product resulting from the reductive alkylation at a temperature of from about 80 to about 300 C. of an equimolar proportion of methyl heptadecyl ketone and aminoethyl ethanolamine.

5. A hydrocarbon distillate normally tending to deteriorate containing a stabilizing concentration of an inhibitor prepared first by the reductive alkylation at a temperature of from about 80 to about 300 C. of an equimolar proportion of a ketone containing from 8 to about 40 carbon atoms and an aminoalkyl alkanolarnine of the following general formula where n is from 2 to 4 and R is selected from the group consisting of hydrogen and an alkyl group of from 1 to 8 carbon atoms, and then reacting from one to two mols of the reductive alkylation product at a temperature of from about to about 200 C. with one mol of a compound selected from the group consisting of an aliphatic dicarboxylic acid, anhydride thereof and the reaction product formed at a temperature of from about to about 300 C., of a terpene having the formula C H and a boiling point within the range of from about 150 to about C. and a compound selected from the group consisting of an alpha,beta-unsaturated aliphatic dicarboxylic acid, anhydride and ester thereof.

6. A hydrocarbon distillate normally tending to deteriorate containing a stabilizing concentration of an inhibitor comprising the product prepared first by the reductive alkylation at a temperature of from about 80 to about 300 C. of an equimolar proportion of a dialiphatic ketone containing from 12 to about 40 carbon atoms and an aminoalkyl alkanolamine of the following general formula where n is from 2 to 4 and R is selected from the group consisting of hydrogen and an alkyl group of from 1 to 8 carbon atoms, and then reacting from one to two rnols of the reductive alkylation product at a. temperature of from about 80 to about 200 C. with one mol of a compound selected from the group consisting of an aliphatic dicarboxylic acid, anhydride thereof and the reaction product formed at a temperature of from about 150 to about 300 C. of a terpene having the formula C H and a boiling point within the range of from about 150 to about 185 C. and a compound selected from the group consisting of an alpha,beta-unsaturated aliphatic dicarboxylic acid, anhydride and ester thereof.

7. Burner oil normally tending to deteriorate containing a stabilizing concentration of an inhibitor prepared first by the reductive alkylation at a temperature of from about 80 to about 300 C. of an equimolar proportion of diheptadecyl ketone and aminoethyl ethanolamine, and then reacting from one to two mols of the reductive alkylation product at a temperature of from about 80 to about 200 C. with one mol of the reaction product formed at a temperature of from about 150 to about 300 C. of a terpene having the formula C H and a boiling point within the range of from about 150 to about 185 C. and maleic anhydride.

8. Burner oil normally tending to deteriorate containing a stabilizing concentration of an inhibitor prepared first by the reductive alkylation at a temperature of from about 80 to about 300 C. of an equimolar proportion of diheptadecyl ketone and aminoethyl ethanolamine, and then reacting from one to two mols of the reductive alkylation product at a temperature of from about 80 to about 200 C. with one mol of the reaction product formed at a temperature of from about 150 to about 300 C. of rosin and fumaric acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,353,192 Sargent et al. July 11, 1944 2,385,518 Isham Sept. 25, 1945 2,388,255 Daskais et al. Nov. 6, 1945 2,464,291 Chenicek Mar. 15, 1949 2,533,723 Dombrow Dec. 12, 1950 2,547,493 Rowland Apr. 3, 1951 2,547,497 Rowland Apr. 3, 1951 (Other references on following page) 15 UNITED STATES PATENTS Thompson et a1. June 9, Caron et a1. July 20, Ambrose et a1. Oct. 26, Chenicek et a1. Nov. 23, Blornberg et a1. Ian. 25, Dazzi May 15,

15 White et a1. Feb. 26, 1957 Strong Apr. 2, 1957 Gee Aug. 26, 1958 Marsh et a1. Sept; 9, 1958 Braaten et a1. -1 Oct. 28, 1958 FOREIGN PATENTS France Apf. 20, 1936

Claims

5. A HYDROCARBON DISTILLATE NORMALLY TENDING TO DETERIORATE CONTAINING A STABILIZING CONCENTRATION OF AN INHIBITOR PREPARED FIRST BY THE REDUCTIVE ALKYLATION AT A TEMPERATURE OF FROM ABOUT 80* TO ABOUT 300*C. OF AN EQUIMOLAR PROPORTION OF A KETONE CONTAINING FROM 8 TO ABOUT 40 CARBON ATOMS AND AN AMINOALKYL ALKANOLAMINE OF THE FOLLOWING GENERAL FORMULA