US3173945A - Itaconamic acids - Google Patents

Description

United States Patent Office 33,173,945 Patented Mar. 16, 1965 3,173,945 TTACGNAMIC ACIDS Harry J. Andress, Ira, Pittman, and Paul Y. C. Gee, Woodbury, N.J., assignors to Socony hiobil Gil Company, Inc, a corporation of New York No Drawing. ()riginal application Oct. 6, H58, Ser. No. 765,296, now Patent No. 3,046,1li2, dated July 24, 1962. Divided and this application st. 24, 1961, Ser. No. 147,175

Claims. (Cl. zed-5m This invention relates to the improvement of non-lubricating pretroleum fractions. It is more particularly concerned with distillate fuel oils containing during prolonged storage periods, to prevent screen-clogging, and to prevent rusting of ferrous metal surfaces.

It is well known that fuel oils are prone to form sludge or sediment during periods of prolonged storage. This sediment, of course, has an adverse effect on burner operation, because it has a tendency to clog screens and nozzles. In addition to sediment formed during storage, most fuel oils contain other impurities, such as rust, dirt, and entrained water. The sediment and impurities tend to settle out on equipment parts, such as nozzles, screens, filters, etc, thereby clogging them and causing the equipment to fail.

A further factor, incident to the storage and handling of fuel oils, is the breathing of storage vessels. This results in the accumulation of considerable amounts of water in the tanks, which presents a problem of rusting in the tanks. Then, when the oil is removed for transportation, sufiicient water may be carried along to cause rusting of ferrous metal surfaces in pipelines, tankers, and the like.

Generally, it has been the practice to overcome the aforedescribed difficulties with a separate additive for each purpose, i.e., with a sediment inhibitor, an antiscreen clogging agent, and an antirust agent. The use 'of several additives, however, gives rise to problems of additive compatibility, thus restricting the choice of additive combinations. In addition, of course, the use of a plurality of additives unduly increases the cost of the fuel. It has been proposed to overcome two difiiculties, e.g., sedimentation and screen clogging, with one additive. Insofar as is known, however, few single addition agents have been found effective against sedimentation, screen and nozzle clogging, and rusting of ferrous metal surfaces.

It has now been found that all three problems, i.e., sedimentation, screen clogging, and rusting, can be solved by the use of a single fuel oil addition agent. It has been discovered that a distillate fuel oil containing minor amounts of certain amic acids and amine salts thereof is effectively inhibited, simultaneously, against all three aforementioned ditficulties.

Accordingly, it is a broad object of this invention to provide a fuel oil having properties improved with a minimum number of addition agents. Another object is to provide a fuel oil having a single additive adapted to inhibit sedimentation, to prevent screen clogging, and to prevent rusting of ferrous metal surfaces with which it comes in contact. A specific object is to provide certain novel amic acids or amine salts thereof and fuel oils containing them. Other objects and advantages of this invention will become apparent to those skilled in the art from the following detailed description.

The present invention provides amic acids of itaconic acid and aliphatic primary and secondary amines having between about 4 carbon atoms and about 39 carbon atoms per molecule and the amine salts thereof with an aliphatic primary amine having between about 4 carbon atoms and about carbon atoms per molecule; and distillate fuel oil containing a minor amount of them, sufiicient to inhibit sedimentation and screen clogging and to prevent rusting of ferrous metal surfaces in contact therewith.

The addition agents contemplated herein are the amic acids of itaconic acid with aliphatic primary and secondary amines having beteween about 4 and about 30 carbon atoms per molecule; and their amine salts with aliphatic primary amines having between about 4 and about 30 carbon atoms per molecule. The amic acids are produced by reacting itaconic acid with the amine reactant in a molar ratio of 1:1, at a temperature varying between about C. and about C. from 2 to 5 hours. The reaction is accompanied by the elimination of water to form amide groups. Thus, it is preferable to carry out the condensation reaction using an azeotrope to remove the Water, such as benzene, toluene, Xylene, etc. The salt of the amic acid can be made readily by warming equimolar quantities of the amic acid and an aliphatic primary amine having between about 4 and about 30 carbon atoms per molecule. The salt-forming amine can be the same amine used in making the amic acid, or it can be a different amine. In the case where the salt-forming amine is the same used in the amic acid, the salt can be made by heating two moles of amine with one mole of acid under temperatures whereby one mole of water is evolved.

The itaconic amic acids can have the structural formulae:

wherein R is an aliphatic hydrocarbon radical having between about 4 and about 30 carbon atoms. Indeed, in the aforedescribed condensation reaction, mixtures of both formulae can be produced. For this reason, and because the amines are often mixtures of amines, the amic acids of this invention are more accurately defined by their method of manufacture.

The amines utilizable in forming the amic acids and the salts thereof are the primary and secondary aliphatic amines having between about 4 and about 30 carbon atoms per molecule. These are the monoamines having a single open chain hydrocarbon group attached to a nitrogen atom. The aliphatic radical can be saturated or unsaturated, and branched-chain or normal chain. Likewise mixtures of these amines, as well as pure amines, can be employed. A very useful and readily available class of primary amines are the tertiary-alkyl, primary, monoamines in which a primary amino (NH group is attached to a tertiary carbon atom; and mixtures thereof. These amines all contain the terminal group,

Non-limiting examples of the amine reactants are t-butyl amine, n-butyl amine, dibutyl amine, t-hexyl primary amine, n-hexylamine, n-octylamine, n-octenylamine, toctyl primary amine, dioctylamine, Z-ethylhexylamine, t-decyl primary amine, n-decylamine, t-dodecyl primary amine, n-undecylamine, dodecenylamine, dodecadienyh amine, tetradecylamine, t-tetradecyl primary amine, t-octadecyl primary amine, dioctadecylamine, hexadecylamine, octadecenylamine, octadecadienyl amine, t-eicosyl primary amine, t-docosyl primary amine, t-tetracosyl primary amine, and t-triacontyl primary amine. The amine reactants can be prepared in several ways well known to those skilled in the art. Specific methods of preparing the t-allryl primary amines are disclosed in the Journal of Organic Chemistry, vol. 20, page 295 et seq. (1955).

Mixtures of such amines can be made from a polyolefin fraction (e.g., polypropylenes and polybutylene cuts) by first hydrating with sulfuric acid and water to the corresponding alcohol, converting the alcohol to alkyl chloride with dry hydrogen chloride, and finally condensing the chloride with ammonia, under pressure, to produce a t-alkyl'primary amine mixture.

The fuel oils that are improved in accordance with this invention are hydrocarbon fractions having an initial boiling point of at least about 100 F. and an end-boiling point no higher than about 750 F., and boiling substantially continuously throughout their distillation range. Such fuel oils are generally known as distillate fuel oils. It is to. be understood, however, that this term is not restrictedv to straight-run distillate fractions. The distillate fuel oils can be straight-run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight-run distillate fuel oils,

naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with well known commercial methods, such as, acid or caustic treatment, hydrogenation, solvent refining, clay treatment, etc.

The distillate fuel oils are characterized by their relatively low viscosities, pour points, and the like. The principal property which characterizes the contemplated hydrocarbons, however, is the distillation range. As mentioned hereinbefore, this range will lie between about 100 F. and about 750 F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.

Particularly contemplated among the fuel oils are Nos. 1, 2, and 3 fuel oils used in heating and as diesel fuel oils, and the jet combustion fuels. The domestic fuel oils generally conform to the specifications set forth in A.S.T.M. Specifications D39648T. Specifications for diesel fuels are defined in A.S.T.M. Specifications D975-48T. Typical jet fuels are defined in Military Specification MIL-F-5624B.

The amount of itaconic amic acid or amine salt of amic acid additives that is added to the distillate fuel oil in accordance with this invention will depend, of course, upon the intended purpose and the particular amic acid or salt selected, as they are not all equivalent in their activity. Some may have to be used in greater concentrations than others to be effective. In most cases, in which. it isdesired to obtain all three beneficial results, namely, to inhibit. sedimentation, to reduce screen clogging, and to prevent rusting of ferrous metal surfaces,

additive concentrations varying between 10 pounds per thousand barrels of oil and about 200 pounds per thousand barrels of oil will be employed. It may not always bedesired, however, to accomplish all three aforementionedresults. In such cases, where it isdesired to effect only one or two results, lower concentrations can be used. Thus, if it is desired only to prevent rust under dynamic conditions, as in a pipeline, it has been found that concentrations as low as about 5 p.p.m., i.e., about one pound of additive per thousand barrels of oil, are effective. In general, therefore, the amount. of amic acid or of amine salt of amic acid that can be added to the distillate fuel oil, in order to achieve a beneficial result, will vary generally between about one pound per thousand barrels of oil'and about 200 pounds per thousand barrels of oil. Preferably, it will vary between about 10 pounds and about 200 poundsper thousand barrels of oil.

If it is desired, the fuel oil compositions can contain other additives for the purpose of achieving other results.

"Thus, for example, there can be present foam inhibitors and ignition and burning quality improvers. Examples of such additives are silicones, dinitropropane, amyl nitrate, metal sulfonates, and the like.

The following specific examples are for the purpose of illustrating the amic acids and salts and the fuel oil compositions of this invention, and of exemplifying the specific nature thereof. It is to be strictly understood, however, that this invention is not to be limited by the particular additives and fuel oils, or to the operations and manipulations described therein. Other amic acids or amine salts thereof and fuel oils, as discussed hereinbefore, can be used, as those skilled in the art will readily appreciate.

. AMIC ACIDS AND SALTS The amine reactants used in the specific working examples are mixtures of pure amines. Amine A is a mixture of primary amines having a carbon atom ofa tertiary butyl group attached to the amino (NH group and containing 12 to 15 carbon atoms per amine molecule and averaging 12 carbon atoms per molecule- This mixture contains, by weight, about percent tertiary dodecyl amine, about 10 percent tertiary penta-' decyl amine, and relatively small amounts, i.e., less than: about 5 percent of amines having less than 12 or more than 15 carbon atoms.

Amine B is a mixture of tertiary-alkyl primary amines averaging 18 to 24 carbon atoms per'molecule. it has a tertiary carbon atom attached to the -NH group. It contains, by weight, about 40 percent t-octadecyl primary amine, about 30 percent t-eicosyl primary amine, about 15 percent t-docosyl primary amine, about 10 percent t-tetracosyl primary amine, and a small amount, less than 5 percent, other amines as high as t-triacontyl primary amine.

Amine C, Amine D, Amine E, Amine F, and Amine G are mixtures or normal aliphatic primary amines having the weight percent compositions setforth in Table I.

Table I Normal Amine Amine Amine Amine Amine Amine C D E F G Dodecyl Tetradecyl Hexadecyl OctadecyL Octadecenyl Octadecadieny EXAMPLE 1 A mixture of 65 grams (0.5 mole) of itaconic acid, gram (0.5 mole) of Amine A, 100 grams of kerosine having a boiling point range from 343 to 519 F., and 50 cc. of benzene was refluxed at 130 C. until the evolution of water ceased. The amount .of water collected during the reaction was 10 cc. (theory 9 cc.). All thebenzene was distilled off. The final product, the Amine A itaconic amic acid, which contained 40% kerosine was clear and fluid at room temperature.

EXAMPLE 2 A mixture of grams (1 mole) of itaconic acid,

300 grams (1 mole) of Amine B, 200 grams of diluent oil (parafilnic oil of 100 S.U.S. at 100 F.) and 100 cc. of benzene was refluxed at 125 C. until water evolution stopped. The amount of water collected during the reaction was 18 cc. (theory 18 cc.). All the benzene was distilled oil. The final product, the Amine B itaconic amic acid, containing 33% diluent oil, was clear and fluid at room temperature.

EXAMPLE 3 A mixture of 54.2 grams (0.4165 mole) of itaconic acid, 50 grams (0.1665 mole) of Amine C, 50 grams (0.25 mole) of Amine A, 100 grams of lrerosine (boiling range 343-519 F.) and 70 cc. of benzene was refluxed at 117-130 C. until water stopped coming over. The amount of water collected during the reaction was 8 cc. (theory 7.5 cc.). All the benzene was distilled off. The final product, the mixed Amine C-An1ine A itaconic amic acid, containing 41% kerosine, was clear and fluid at room temperature.

EXAMPLE 4:

A mixture of 54.2 grams (0.4165 mole) of itaconic acid, 50 grams (0.1665 mole) of Amine D, 50 grams (0.25 mole) of Amine A, 100 grams of xylene and 75 cc. of benzene was refluxed at 120 C. until water stopped coming over. The amount of water collected during the reaction was 8.5 cc. (theory 7.5 cc.). All the benzene was distilled over. The final product, the mixed Amine D-Aminc A itaconic amic acid, containing 41% xylene was clear and fluid at room temperature.

EXAMPLE 5 A mixture of 32.5 grams (0.25 mole) of itaconic u acid, 75 grams (0.25 mole} of Amine C, 50 grams of xylene and 50 cc. of benzene was refluxed at 125 C. until water stopped coming over. The amount of water collected during the reaction was 4.5 cc. (theory 4.5 cc.). All the benzene was distilled off. The final product, the Amine C itaconic amic acid, which contained 33% xylene was clear and fluid at room temperature.

EXAMPLE 6 A mixture of 32.5 grams (0.25 mole) of itaconic acid, 32.25 grams (0.25 mole) of Amine E, 50 grams xylene and 60 cc. benzene was refluxed at 100105 C. until the evolution of water ceased. The amount of water collected during the reaction was 4.5 cc. (theory 4.5 cc.). All the benzene was distilled oil. The final product, the Amine E itaconic amic acid, which contained 46% xylene was clear and fluid at room temperature.

EXAMPLE 7 mixture of 65 grams (0.5 mole) of itaconic acid, 97.5 grams (0.5 mole) of Amine F, 100 grams of xylene and 75 cc. of benzene was refluxed at 100 C. until water stopped coming over.

The amount of water collected during the reaction was cc. (theory 9 cc.). All the benzene was distilled off. The final product, the Amine F itaconic amic acid, which contained .0% xlyene was clear and fluid at room temperature.

EXAMPLE 8 A mixture of 65 grams (0.5 mole) of itaconic acid, 140 grams (0.5 mole) of Amine G, 140 grams of xylene and 75 cc. of benzene was refluxed at 115 C. until water stopped coming over. The amount of water collected during the reaction was 10 cc. (theory 9 cc.). All the benzene distilled oil. The final product, the Amine G itaconic amic acid, which contained 41% xylene was clear and fluid at 50 C. and solidifying at room temperature.

EXAMPLE 9 A mixture of 43.5 grams /3 mole) of itaconic acid, 150 grams /3 mole) of Amine H, 100 grams of xylene and 75 cc. of benzene was refluxed at 125 C. until water stopped coming over. The amount of water collected during the reaction was 6 cc. (theory 6 cc.). All the benzene was distilled off. The final product, the Amine H itaconic amic acid, which contained 35% xylene was clear and fluid at room temperature.

EXAMPLE 10 A mixture of 32.5 grams (0.25 mole) of itaconic acid, 50 grams (0.25 mole) of Amino A, grams of xylene and 50 cc. of benzene was refluxed at 125 C. to form an Amine A itaconic amic acid. The temperature was held at 125 C. until water stopped coming over. The amount of water collected during the reaction was 4.5 cc. (theory 4.5 cc.). To the Amine A itaconic amic acid was added at room temperature with stirring 75 grams (0.25 mole) of Amine C to form an amine salt. The mixture was stirred at 5 C. for 3 hours. The product, the Amine C salt of Amine A itaconic amic acid, was distilled at C., under a pressure of 5 mm. of mercury, until no more benzene and xylene came over.

EXAMPLE 1 1 A mixture of 32.5 grams (0.25 mole) of itaconic acid, 75 grams (0.25 mole) of Amine C, 75 grams kerosine (boiling range 343-519 F.) and 75 cc. of benzene was refluxed at 135 C. to form an Amine C itaconic amic acid. The temperature was held at 135 C. until water stopped coming over. The amount of water collected during the reaction was 6 cc. (theory 4.5 cc.). All the benzene was distilled off. To the Amine C itaconic amic acid was added at room temperature with stirring 50 grams (0.25 mole) of Amine A to form an amine salt. The mixture was stirred at 8590 C. for 3 hours. The final product, the Amine A salt of Amine C itaconic amic acid, winch contained 33% kerosine was clear and fluid at room temperature.

EXAMPLE 12 A mixture of 65 grains (0.5 mole) of itaconic acid, 149 grams (0.5 mole) of Amine D, grams of xylene and 75 cc. of benzene was refluxed at C. to form an Amine D itaconic amic acid. The temperature was held at C. until water stopped coming over. The amount of water collected during the reaction was 9 cc. (theory 9 cc.). All the benzene was distilled off. To the Amine D itaconic amic acid was added at room temperature with stirring 100 grams (0.5 mole) of Amine A to form an amine salt. The mixture was stirred at 75 C. for 2 hours. The final product, the Amine A salt of Amine D itaconic amic acid, which contained 25% xylene was clear and fluid at room temperature.

EXAMPLE ,13

A mixture of 65 grams (0.5 mole) of itaconic acid, 68 grams (0.5 mole) of Amine E, 100 grams of xylene and 75 cc. of benzene was refluxed at 115 C. to form an Amine E itacc-nic amic acid. The temperature was held at 115 C. until water stopped coming over. The amount of water collected during the reaction was 9 cc. (theory 9 cc.). All the benzene was distilled oil". To the Amine E itaconic amic acid was added at room temperature with stirring 100 grams (0.5 mole) of Amine A to form an amine salt. The mixture was stirred at 75 C. for 2 hours. The final product, the Amine A salt of Amine E itaconic amic acid, which contained 31% xylene was clear and fluid at room temperature.

EXAMPLE 14 A mixture of 65 grams (0.5 mole) of itaconic acid, 97.5 grams (0.5 mole) of Amine F, 100 grams of xylene and 50 cc. of benzene was refluxed at 115 C. to form an Amine F itaconic amic acid. The temperature was held at 115 C. until water stopped coming over. The amount of water collected during the reaction was 9 cc. (theory 9 cc.). All the benzene was distilled off. To the Amine F itaconic amic acid was added at room temperature with stirring 100 grams (0.5 mole) of Amine A to form an amine salt. The mixture was stirred at 75 C. for 2 hours. The final product, the Amine A salt of Amine G itaconic amic acid, which contained 29% xylene was clear and fluid at room temperature.

EXAMPLE 15 A mixture of 65 grams (0.5 mole) of itaconic acid, grams (0.5 mole) of Amine C, 100 grams of xylene and F! Z 50 cc. of benzene was refluxed at 125 C. to form an Amine G itaconic amic acid. The temperature was held at 125 C. until water stopped coming over. The amount of water collected during the reaction was 9 cc. (theory 9 cc.). All the benzene was distilled off. To theArnine G itaconic amic acid was added at room temperature with stirring 100 grams (0.5 mole) of Amine A to form an amine salt. The mixture was stirred at 75 C. for 2 hours. The final product, the Amine A salt of Amine G itaconic amic acid, which contained 26% xylene was clear and fluid at room temperature.

EXAMPLE 16 A mixture of 43.3 grams /a mole) of itac'onic acid, 66.7 grams /3 mole) ofAmine A, 204 grams of diluent oil (paraflinic oil of 100 S.U.S. at 100 F.) and 75 ccof benzene was refluxed at 125 C. to form an Amine A itaconic amic acid. The temperature was held at 125 C. until water stopped coming over. The amount of water collected during the reaction was 6 cc. (theory 6 co}. All the benzene. was distilled off. To the Amine A itaconic amic acid was added at room temperature with stirring 100 grams /3 mole) of Amine B to form an amine salt. The mixture was stirred at 85-95" C. for 3 hours. The final product, the Amine B salt of Amine A itaconic amic: acid, which contained 50% diluent oil was clear and fluid at room temperature.

SEDIMENTATION The test used to determine the sedimentation characteristics of the fuel oils is the 110 F. Storage Test. In this test, a 500-milliliter sample of the fuel oil under test is placed in a convected oven maintained at 110 F. for a. period of 12 Weeks. Then, the sample is removed from the oven and cooled. The cooled sample is filtered. through a tared asbestos filter (Gooch crucible) to remove insoluble matter. The weight of such matter in milligrams is reported as the amount of sediment. A sample of the blank, uninhibited oil is run along with a fuel oil blend under test. The effectiveness of a fuel oil containing an inhibitor is determined by comparing the weight of sediment formed in the inhibited oil with that formed in the uninhibited oil.

The additives described in the examples were blended in test fuel oil and the blends were subjected to the 110 F. Storage Test. The test results comparing the blended fuels and uninhibited fuels are set forth in Table II. The test fuel oil was a blend of 60 percent distillate stock obtained from continuous catalytic cracking and 40 percent straight-run distillate stock. It has a boiling range of be tween about 320 F. and about 640 F. and is a typical No. 2 fuel oil. 7

Table II [110 F. Storage Test-12 weeks] 6 hours.

8 SCREEN CLOGGING The anti-screen clogging characteristics of a fuel oil were determined as follows: The test is conducted using a isundstrand V3 or S1 home fuel oil burner pump with a self-contained 100-mesh monel metal screen. About 0.05 percent, by weight, of naturally-formed fuel oil :sediment, composed of fuel oil, water, dirt, rust, and or- .ganic sludge is mixed with 10 liters of the fuel oil. This .mixture is circulated by the pump through the screen for Then, the sludge deposit on the screen is washed off with normal pentane and filtered through a timed Gooch crucible. After drying, the material in Gooch crucible is washed with a 50 (volume) acetone-methanol mixture. The total organic sediment is obtained by evaporating the pentane and the acetone- :methanol filtrates." Drying and weighing the Gooch crucible yields the amount of inorganic sediment. The sum of the organic and inorganic deposits on the screen can be reported in milligrams recovered or converted mto percent screen clogging.

' Blends of the additives of the examples were prepared an the raforedescribed test fuel oil and subjected to the Screen Clogging Test. Results are set forth in Table III.

T able III [Screen clogging] Concn, Screen Additive of Example lbs/1,000 Clogging,

, bbls. Percent Blank 100 l- 100 32 2- 25 2 3- 50 14 4- 50 3 5- 50 6 6 100 9 7- 50 13 8. 50 2 9 25 8 10. 100 5 l1 25 10 RUSTING The method used for testing anti-rust properties of the fuel oils was the A.S.T.M. Rust Test D665 operated for 48 hours at 80 F. using distilled water. This is a dynamic test that indicates the ability to prevent rusting of ferrous metal surfaces in pipelines, tubes, etc.

Blends of the additives described in the examples in the aforedescribed test fuel oil were subjected to the A.S.T.M. gust Test D-665. Pertinent data are set forth in Table Additive of Example Ooncn, lbs. Sediment Table IV /1,000 bbls. nag/liter [A.S.T.M. Rust; Test D-665] Blank 10 Conen Rust Test 25 6 Additive of Example parts per Result Blank 25 V 3 million 1 B1 1 1 t F il. Blank 49 1. 2. 5 P385. 5O 37 2 50 Pass. Blank 5 3. 10 Pass. 25 2 4 10 Pass. 25 2 5 2.5 Pass. Blank a4 6. 50 Pass. 24 7 5 Pass. Blank 49 8.- 5 Pass. 1 100 10 9-"- 50 Pass. Blank 141 10. 50 Pass. 100 49 11- 2. 5 Pass. Blank 6 12- 10 Pass. 2 50 2 7 13 10 Pass. Blank" 34. 14. 5 Pass. 13 50 8 15- 10 Pass. Blank 6 16- 25 Pass. 4 50 1 15 5 1 16. 25 3 The Static Rust Test simulates conditions encountered 7 in storage tanks, such as, the home fuel Oll storage tank.

In this test, a strip of 16-20 gauge sand blasted steel plate is placed in a cl ar quart bottle. The length of the strip is sufiicient to reach from the bottom of the bottle into the neck of the bottle without interfering with the cap. One hundred cc. of synthetic sea Water with pH adjusted to 5 (A.S.T.M. D665) and 750 cc. of test oil are placed in the bottle. The bottle is capped tightly, shaken vigorously for one minute, and permitted to stand quietly at 80 F. for 21 days. At the end of that time, the amount of rust that occurs on the surface of the plate immersed in the water is used as a measure of efiectiveness of the fuel to inhibit rushing in storage vessels. It is generally preferred that no more than 5 percent of the surface should be rusted. This test is much more severe than the A.S.T.M. Rust Test. Many additive compositions that pass the A.S.T.M. test fail in the static test. On the other hand materials that pass the static test always pass the A.S.T.M. test.

Blends of the additives of the examples in the aforedescribed test fuel oil were subjected to the Static Rust Test. Pertinent results are set forth in Table V.

Table V [Static rust test] Gone-n, Percent Additive 01 Example lbs/1,000 rusting bbls.

Blank 100 1 35 2 50 30 3-- 50 0 25 u 5 25 0 7 25 0 a 50 0 q 50 10 10 50 11 10 0 19 50 1 1 1 so 50 16 75 0 It will be apparent, from the data set forth in Tables 11 through V, that the amic acids of this invention and amine salts thereof are highly etfective to reduce sedimentation and screen clogging and to inhibit rusting of ferrous metal surfaces. As is to be expected results will vary among specific materials used. In order to accomplish any given improvement, many of the additives can be used in relatively small amounts, as for dynamic rust prevention. If, on the other hand, it is desired to accomplish all the aforementioned beneficial results, this can be accomplished at the practical additive concentration of 50400 pounds per thousand barrels of fuel oil.

The present application is a division of copending application, Serial No. 765,296, filed October 6, 1958, now US. Patent No. 3,046,102.

Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as

1% those skilled in the art will readily understand. Such variations and modifications are considered to be within the purview and scope of the appended claims.

What is claimed is:

1. A material selected from the group consisting of amic acid products obtained by reacting (A) itaconic acid with primary alkyl amines having a tertiary carbon atom attached to the amino group and containing from about 4 to about 30 carbon atoms per molecule, and (B) salts obtained by reacting A with aliphatic hydrocarbyl amines having from about 4 to about 30 carbon atoms per molecule.

2. Amie acid products obtained by reacting itaconic acid with primary allryl amines having a tertiary carbon atom attached to the amino group and containing from about 4 to about 30 carbon atoms per molecule.

3. Salts obtained by reacting the amic acid products of itaconic acid and primary alkyl amines having a tertiary carbon atom attached to the amino group and containing from about 4 to about 30 carbon atoms per molecule, with aliphatic hydroearbyl amines having from about 4 to about 30 carbon atoms per molecule.

4. Arnie acid products obtained by reacting an itaconic acid with a mixture of primary alkyl amines having a tertiary carbon atom attached to the amino group and containing from about 12 to about 15 carbon atoms per molecule and averaging about 12 carbon atoms per molecule.

5. Salts obtained by reacting the amic acid products of itaconic acid and a mixture of primary allryl amines having a tertiary carbon atom attached to the amino group and containing from about 12 to about 15 carbon atoms per molecule and averaging about 12 carbon atoms per molecule, with a mixture of primary alkyl amines having a tertiary carbon atom attached to the amino group and containing from about 12 to about 15 carbon atoms per molecule and averaging 12 carbon atoms per molecule.

References Eited in the file of this patent UNITED STATES PATENTS 2,604,449 Bryant et al July 22, 1952 2,718,503 Rocchini Sept. 20, 1955 2,879,253 Coover Mar. 24, 1959 2,908,711 Halter et a1 Oct. 13, 1959 2,944,969 Stromberg et a1. June 12, 1960 2,976,216 De Mytt Mar. 21, 1961 3,031,282 Andress et a1. Apr. 24, 1962 FOREIGN PATENTS 859,304 Germany Dec. 11, 1952 449,081 Great Britain June 10, 1936 OTHER REFERENCES Holmberg et al.: Chem. Abst, vol. 35, 1941, column Rohm and Haas Company, TertiaryAlky1 Primary Amines, October 1956, pages 3, 17-21.

UNITED STATES PATENT OFFICE CERTIFICATE OF (ZORRECTION Patent No. 3,173,945 March 16, 1965 Harry J, Andress, Jr. et. al.

It is hereby certified that error appears in-the above numbered patent reqiiring correction and that the said Letters Patent should read as oorreotedbelow.

Column 1, line 12, after "containing" insert additives adapted to inhibit the appearance of sediment column 4, line 33, for "or" read of column 5, line 51, for "100 Cu" read 110 C. column 6, line 75, for "Amine C" read "Amine G Signed and sealed this 24th day of August 1965;

SEAL) nest: IRNEST W. SWIDER EDWARD J. BRENNER nesting Officer Commissioner of Patents

Claims (1)

1. A MATERIAL SELECTED FROM THE GROUP CONSISTING OF AMIC ACID PRODUCTS OBTAINED BY REACTING (A) ITACONIC ACID WITH PRIMARY ALKYL AMINES HAVING A TERTIARY CARBON ATOM ATTACHED TO THE AMINO GROUP AND CONTAINING FROM ABOUT 4 TO ABOUT 30 CARBON ATOMS PER MOLECULE, AND (B) SALTS OBTAINED BY REACTING A WITH ALIPHATIC HYDROCARBYL AMINES HAVING FROM ABOUT 4 TO ABOUT 30 CARBON ATOMS PER MOLECULE.