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Publication numberUS3197510 A
Publication typeGrant
Publication dateJul 27, 1965
Filing dateMar 1, 1962
Priority dateMar 1, 1962
Publication numberUS 3197510 A, US 3197510A, US-A-3197510, US3197510 A, US3197510A
InventorsHenryk A Cyba
Original AssigneeUniversal Oil Prod Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
N1-secondary-alkyl-aminoalkyl alkanolamines
US 3197510 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,197,510 N SEQGNDARY-ALKYLAMINQALKYL ALKANOLAMINES Henryl; A. Cyha, Chicago, lilL, assignor to Universal Oil Products Company, Des Plaines, Ill., a corporation of Eclaware No Drawing. Filed Mar. 1, 1962, Ser. No. 176,822 6 Claims. (Cl. 26ll584) This is a continuation-in-part of copending application Serial No. 756,521, filed August 22, 1958, nOW abandoned which, in turn, is a continuation-in-part of application Serial No. 655,199, filed April 26, 1957, now Patent 3,018,173, dated January 23, 1962. The present invbntion relates to a novel composition of matter which is particularly useful as an additive for the stabilization of organic compounds and, more particularly, for use in preventing deterioration of organic compounds in storage, during transportation or in use.

The novel additives of the present invention are particularly advantageous for use in the stabilization of hydrocarbon distillates and serve 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 beneficient 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 L r' blends or straight run and cracked fuel OllS 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 diesel fuel, the deterioration tends to form varnishand 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 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 case 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 corrodes 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 novel composition of matter of the following formula:

where R and R are alkyl and the total number of carbon atoms in R and R is from 2 to about 50, n is from 2 to 4, and R" is selected from the group consisting of hydrogen and alkyl of from 2 to 8 carbon atoms.

In a specific embodiment the present invention relates to the novel compound of N -l-heptadecyloctadecylaminoethyl ethanolamine.

The novel compounds of the present invention comprise the reductive alkylation product of a ltetone and an aminoalkyl alkanolamine or" 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 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, polyarnides, polyurethanes and epoxy resins, which contain function groups including, for example, hydroXyl, carboxyl, isocyanate 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 novel compound is prepared by the reductive alkylation of a ketone and an aminoalkyl allranolamine. In one embodiment the ketone may contain from 3 to about 50 carbon atoms. When used as an additive in hydrocarbon distillates, the ketone preferably contains at least 8 carbon atoms and more preferably at least 12 carbon atoms, and usually will contain from about 8 and preferably from about 12 to about 40 carbon atoms, although ketones containing up to about 50 carbon atoms may be employed.

Any suitable ketone is used in accordance with the present invention. A preferred ketone comprises an aliphatic ketone. Illustrative aliphatic ketones for use in the present invention include acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl emyl ketone, methyl hexyl ketone, methyl heptyl ketone, methyl octyl ketone, methyl nonyl ketone, diethyl ketone, ethyl propyl ketone, ethyl butyl ketone, ethyl amyl ketone, ethyl hexyl ketone, ethyl heptyl ketone, ethyl octyl ketone, dipropyl ketone, propyl butyl ketone, propyl amyl ketone, propyl hexyl ketone, propyl heptyl ketone, dibutyl ketone, butyl amyl ketone, butyl hexyl ketone, diamyl ketone, etc.

Preferred illustrative aliphatic ketones include methyl decyl ketone, methyl undecyl ketone, methyl dodecyl ketone, methyl tridecyl 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, methyl pentatriacontyl 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 nonadecyl ketone, ethyl eicosyl 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, propyl eicosyl 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 nonacosyl ketone, propyl triacontyl ketone, propyl hentriacontyl ketone, propyl dotriacoutyl ketone, propyl tritriacontyl ketone, propyl tetratriacontyl ketone, propyl pentatriacontyl ketone, propyl hexatriacontyl ketone, etc., butyl octyl ketone, butyl nonyl ketone, butyl decyl ketone, butyl undecyl ketone, butyl 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.

Additional illustrative aliphatic ketones include dihexyl ketone, diheptyl ketone, dioctyl ketone, dinonyl ketone, didecyl ketone, diuudecyl ketone, didodecyl ketone, ditridecyl ketone, ditetradecyl ketone, dipcntadecyl ketone, dihexadecyl ketone, diheptadecyl ketone, dioctadecyl ketone, dinonadecyl ketone, dieicosyl ketone, etc, as well as hetones 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 lcetones containing at least 12 carbon atoms are available as mixtures which are either products or by-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 expense of separating specific compounds in pure state. One such mixture available commercially as a primary product of the process is stearone which is diheptaclecyl ketone.

While the alkyl ketones are preferred, in some cases, ketones containing unsaturation in the aliphatic group may be employed. Also, aromatic ketones, aromatic aliphatic ketones, cycle-aliphatic ketones, cycle-aliphatic aiiphatic ketones and cycloaliphatic aromatic ketones may be utilized. Furthermore, while generally it is preferred to utilize the same ketone in forming the reductive alkylation product, it is understood that a mixture of ketones may be employed. In another embodiment, 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 Lilli!- ent ketones meeting the requirements hereinbefore set forth may be employed. However, it is understood that the diiferent ketones are not necessarily equivalent for use in preparing the reductive alkyiation 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 reduc tive allrylation with the hereinbefore described ketone is illustrated by 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.

Where R in the above general formula is hydrogen, illustrative compounds include aminoethyl ethanolamine, aminopropyl propanolamine, aminobutyl butanolamine, aminopropyl ethanolamine, aminobutyl ethanolamine, aminoethyl propanolamine, aminobutyi propanolaminc, aminoethyl butanolamine and aminopropyl butanolaminc. In general, it is preferred that both R substituents 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, alkylcyclohexyl, etc. In mother embodiment, the hydrocarbon group is selected from alkcnyl, allrenyl aryl, arylallrenyl, 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 1-aminoethylamino-propanol-Z, l-aminoethylamino-butanol-Z,

1-aminoethylamino-pentanol-Z, l-aminoethylamino-hexanol-Z, 1-aminoethylarnino-heptanol-Z, 1-aminoethylamino-octanol-Z, etc., l-aminoethylamino-butanol-3, 1-an1inoethylamino-pentanol-3, 1-aminoethylamino-hexanoi-3, 1-aminoethylamino-heptanol-3, 1-aminoethylamino-octanol-3, etc., 1-aminoethylamino-pentauni-4, 1-'tminoethylamino-hexanol-4, 1-aminoethylamino-heptanol-Al, 1-aminoethylamino-octanoli, etc., 1-aminopropylamino-propanol-Z, 1-aminopropylamino-butanol-Z, 1-aminopropylamino-pentanol-Z, 1-aminopropylarnino-hexanol-Z, 1-aminopropylamino-heptanol-2, laminopropylamino-octanol-Z, etc, 1-aminopropylamino-butanol-3, 1-aminopropylarnino-pentanol-3, 1-aminopropylamino-hexanol-3, 1-aminopropylamino-heptanol-3, 1-aminopropylamino-octanol-3, etc., 1-aminoethylamino-pentanol-4, 1-aminopropylamino-heXanoll, 1-aminopropylamino-heptanoll, 1-aminopropylarninooctanol-4, otc., 1-aminobutyiamino-propanol2, l-aminobutylamino-butanol-Z, 1-aminobutylamino-pentanol-Z, l-arninobutylamino-hexanol-Z, 1-aminobutylamino-heptanol-Z, 1-arninobutylarnino-octanol-Z, etc, l-aminobutylamino-butanol-B, 1-aminobutylamino-peutancl--3, l-aminobutylamino-hexanol-Z, 1-aminobutylamino-heptanol-3, 1-aminobutylamino-octanol-3, etc., 1-aminobutylamino-pentanoll, 1-aminobutylamino-heXanol-4, 1-aminobutylaminoheptanol-4-, 1-aminoethylamino-octanol-4, etc.

Where R is an aryl group, illustrative compounds include Laminoethylamino-2-phenyl-ethanol-2, l-aminoethylamino 2 tolyl-propanol-3, l-aminoethyamino-Z- phenyl-butanol-4, 1 aminoethylamino-Z-tolyl-hexanol-Z, 1-aminoethylamino-Z-phenyl heptanol-3, l-aminoethylamino 2-tolylctanol-4-, l-aminopropylamino-Z-phenylethanol-2, 1-aminopropylarnino-Z-tolyl-propanol-3, etc.

It will be noted that a number of different aminoalkyl allzanolamines may be utilized in preparing the reductive alkylation products. it is understood that the diiterent 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 allrylation of the ketone and aminoalkyl alkanolamine may be effected in any suitable manner. In general, the reaction is effected using an equimolar proportion of lretone 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 effected in two steps. In the first step, a Schifis base of the ketone and aminoalltyl alkanolamine is prepared, and the Schifis base then is reduced to the desired product. in the first step, the ltetone and aminoalkyl alkanolamine 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, ethyl-benzene, 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 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 Schiffs 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 kieselguhr 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 there 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 0, 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 hydro-gen. A preferred catalyst comprises the platinum-containing catalyst herein- :before 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 80 and about 300 C. and preferably between about 100 and about 250 C.,'and the hydrogen pressure gen erally is from about 100 to about 3000 pounds square inch.

The reductive allcylation product 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 alliylation product and/ or further reaction product and is recovered in admixture with 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 reoovered in the manner hereinbefore set forth, it is understood that the same or ditte-rent solvent may be commingled with the mixture to form a solution of the desired concentration.

The concentration of additive to be used in 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 5% by weight or more and more specifically is used in a concentration or" from about 0.0001% to about 1% by Weight of the substrate. The additive may be used along with other additives which per 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 substarate, it may be added thereto in the desired amount and the resultant mixture suitably agitated in order to obtain intimate mixing of the additive in the substrate. When he 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 beneficient. 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 efiuent 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 N -l-heptadccyloctadecyl-aminoethyl ethanolarnine, the additive of this example, was prepared by the reductive alkylation of stearone and aminoethyl ethanolamine. As hereinbefore set forth, stearone is diheptadecyl ketone. The reductive alkylation was prepared in two steps as follows: 538 g. (one mol) of stearone and 109 g. (one mol+5% excess of aminoethyl ethanolamine were refluxed in 100 g. of toluene. 18.6 cc. of water was recovered from the reaction. The resultant Schifis base was reduced in a rocker bomb at 140 C. with 125 atmospheres of hydrogen in the presence of 100 g. 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 mol 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 pased through a filter, and the time required to develop a differential pressure across the filter of in. Hg is determined. It is apparent that the longer the time, the more efiective is the additive. 'rlowever, with a very effective additive, the time to reach a differential pressure across the filter of 25 in. H 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 oil and evaluated in the Erdco Test. After 300 minutes, the differential pressure across the filter was 0.2 in. Hg. On the other hand, a control sample (not containing this additive) developed a differential presure 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 of the 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.

6% EFL/li H N -1unethyloctadecyl-aminoethyl ethanolamine, the additive of this example, was prepared by the two-step reductive al tylation of methyl heptadecyl lretone and aminoethyl ethanolamine. 2552 g. (one mol) of methyl hcptathe i kctone and 109 g. (one mol) of aminoethyl ethanolamine and g. of xylene were refluxed, with the evolution of 22 cc. of water. The resultant Schifrs base with 200 g. of toluene was reduced in the presence of 100 g. 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 ambergreasy 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 212"l4 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 paleorange rnicrocrystalline waxy solid. its specinc gravity at 60 F. is 0.8849.

0.001% by weight of the total reductive alkylated prodnot 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 30-0 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.

EXAl-vilLE Hf N -1-methylhcptyl-aminoethyl ethanolamine, the additive of this example, was prepared by the two-step reductive alkylation of methylhexyl ketone and aminoethyl ethanoiaminc. The reductive allcylation was effected in substantially the same manner as hereinbefore set forth. 520 g. (4.06 mols) of methylhexyl ketone was refluxed with 208 g. (2 mols) of aminoethyl ethanolamine. The reduction of the Schiffs base was effected at C. in the presence of 100 atmospheres of hydrogen in a rocker bomb for six hours using 100 g. of the alumina-platinumcombined halogen 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 1724 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 at 60 F. of 0.8984 and an index of refraction at 20 C. of 1.4 630.

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

10% of the same additive (1 g.) was mixed together with commercial epoxy resin Epon 828. The mixture was cured at :2 C. for 1%. hours. After this time, the Epon 828 was cured to a somewhat soft mass. The example indicates that the alltylation product of aminoethyl ethanolamine with methylhexyl ketone acts as curing agent for epoxy resins.

EXAMPLE IV 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 the additive prepared as described in Exam- T able I.-Time in seconds for successive 400 cc.

portions to pass Additive 1 2 3 1 Color None 37 70 125 32. 5 Example I 25 30 36 43. 0

From the data in the above table, it will be noted that the sample of oil which did not contain an additive required 125 seconds for the third portion to pass through the screen, Whereas the third portion of the sample containing the additive passed through the screen in 36 seconds. The color of the oil was improved through the use of the additive as shown by the data in the above table.

EXAMPLE V As hereinbefore set forth, the additive of the present invention also serves 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 are 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 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 eltectively reduced corrosion.

EXAMPLE VI N -1-mcthylhexadecyl-aminoethyl ethanolamine, the compound of this example, was prepared by the two-step reductive alkylation of methyl pentadecyl ketone and aminoethyl ethanolamine. 508 g. (2 mols) of methyl pentadecyl ketone were refluxed with 218 g. (2 moles-{- 10 g. excess) of aminoethyl ethanolarnine. base was reduced at 160 C. and 100 atmospheres of The Schiffs 5 hydrogen for 6 hours in the presence of 100 g. of the alumina-platinum-combined halogen catalyst previously described. The reduced product was then heated at 155 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 of the total, had a boiling point of 201203 C. This is a pale-tan, almost white liquid, solidifying or melting at about 2224 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 VI I N -1-methylethyl-aminopropyl propanolamine is prepared in one step by the reductive alkylation of one mol of acetone with one mol of aminopropyl propanolamine at 150 C. and atmospheres of hydrogen in the pres ence of platinized alumina catalyst.

EXAMPLE VII-I N 1-methylpropyl-aminoethyl propanolamine is prepared by the reductive alkylation of one mol of methylethyl ketone with one mol of aminoethyl propanolamine. The reductive alkylation is effected by refluxing the reactants in benzene solvent and removing the water of reaction. The resultant Schiffs base is hydrogenated at C. in the presence of nickel catalyst.

EXAMPLE IX N -1-isobutyl-3-methylbutyl-arninoethyl ethanolamine is prepared by the single step process of reacting one mol of diisobutyl ketene with one mol of aminoethyl ethanolamine in the presence of an alumina-platinum catalyst and 100 atmospheres of hydrogen at C. The water formed in the reaction is separated from the reactor effiuent product and the effluent product is further fractionated to recover N -l-isobutyl-3-methylbutyl-aminoethyl ethanolamine.

I claim as my invention:

It. A compound of the following formula:

where R and R are alkyl and the total number of carbon atoms in R and R is from 2 to about 50, n is from 2 to 4, and R" is selected from the group consisting of hydrogen and alkyl of from 2 to 8 carbon atoms.

. N -1-heptadecyloctadecyl-aminoethyl ethanolamine. N -l-methyloctadecyl-aminoethyl ethanolamine.

. N -1-methylhexadecyl-aminoethyle-thanolaminc.

. N -1-methylheptylaaminoethyl ethanolamine.

. N -l-methylpropyl-aminoethyl ethanolamine.

References Cited by the Examiner UNITED STATES PATENTS 2,362,464 11/44 Britten et al 260583 X CHARLES E. PARKER. Primary Examiner.

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