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Publication numberUS3282836 A
Publication typeGrant
Publication dateNov 1, 1966
Filing dateMar 22, 1963
Priority dateMar 22, 1963
Publication numberUS 3282836 A, US 3282836A, US-A-3282836, US3282836 A, US3282836A
InventorsHoward M Lurton, James R Miller
Original AssigneeShell Oil Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Corrosion resistant liquid hydrocarbons containing mixture of alkyl succinic acid and polyamine salt thereof
US 3282836 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

3,282,836 CORROSION RESESTANT LIQUID HYDROCAR- BONS CONTAINING MIXTURE OF ALKYL UCCENIC ACID AND POLYAMINE SALT THEREOF James R. Miller, Florissant, Mo., and Howard M. Lurton, Dow, 111., assignors to Shell Oil Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Mar. 22, 1963, Ser. No. 267,341. 12 Claims. (Cl. 252-345) This invention relates to new and improved multifunctional liquid hydrocarbon composition such as gasoline, fuel oil, and mineral lubricating oil compositions. More particularly the invention is directed to above mentioned liquid hydrocarbon compositions possessing excellent corrosion (vapor and liquid) inhibiting properties as well as anti-stalling properties attributed to formation of ice on engine parts.

It is well known that corrosion due to chemical or mechanical means of engine parts results in ineflicient engine operation and necessitates replacing of corroded parts, thus increasing the cost of effective engine operation. Corrosion of metal parts is particularly aggravated by ice formation on the throttle plate, carburetor and other engine parts which not only causes corrosion but engine stalling as well, which is an inconvenience and safety hazard.

It is an object of this invention to provide and improve liquid hydrocarbon compositions with effective corrosion inhibitors. Another object of this invention is to provide improved fuel (gasoline and fuel oil) compositions which prevent corrosion of metal parts. Still another object of this invention is to provide improved anti-clogging, antistalling and anti-corrosive fuel compositions. Also another object of this invention is to provide mineral lubricating oil compositions with improved vapor phase and liquid phase corrosion inhibiting properties. Other objects of this invention will be apparent from the following description of the invention.

It has now been found that improved corrosion inhibited liquid hydrocarbon compositions such as gasoline,

fuel oil and mineral lubricating oil compositions can be rendered non-corrosive by addition thereto from about 0.0001% to about 2% and preferably from about 0.0005 to about 0.1% by weight of an oil-soluble additive mixture of (1) a C alkyl or alkenyl succinic acid and (2) certain polyamine salts of C alkyl or alkenyl succinic acid, the proportions of the tWo additives varying from about 1% to about 20% of the C alkyl or alkenyl succinic acid and from about 80% to about 99% of the polyamine salt of C alkyl or alkenyl succinic acid. By polyamine is meant an N-alkyl substituted alkylene polyamine and N-amino or N-hydroxy alkyl substituted irnidazoline.

The amines of group (1) namely the N-alkylated polyamines include N-C alkyl propylene diamine, N-C alkyl ethylene diamine, NC alkenyl propylene diamine, N-C alkenyl dipropylene triamine, ocentyl diethylene triamine, decenyl triethylene tetraamine, octadecenyl propylene diamine, tetrapropenyl propylene diamine, and other polyamines of this type are commercially available under the trade name Duomeens and include Duomeen C where R is derived from cocoanut, Duomeen S States Patent 3,282,836 Patented Nov. 1, 1966 where R is derived from soya, Duomeen T where R is derived from tallow; oxyalkylated Duomeen S where R is heptadecenyl radical or polyamine such as Amine OLT (tetrapropenyl ethylene diamine) and the like.

The imidazolines are well known compounds which may be prepared by the methods described in Chemical Reviews, vol. 54, No. 4, August 1954 under the title The Chemistry of Imidazoles by Form and Riebsomer or they may be prepared by the method described in US. Patent 2,267,965. Examples of suitable compounds are l-aminoethyl-Z-undecyl imidazoline, l-aminoethyl-Z-heptadecenyl imidazoline, l-aminoethyl-2-heptadecyl imidazoline, 1 aminoisopropyl 2 heptadecyl-Z-methyl imidazoline, l-aminobutyl-2-pentadecyl imidazoline, 1-2-(2- aminoethyl)-aminoethyl-2-pentadecyl imidazoline. Aminoalkyl substituted imidazolines of this type are commercially available under the trade name of Nalcamines such as Nalcamine G32 which is 1-(2-aminoethyl)-2-n- C alkyl imidazoline. Another preferred aminoalkyl imidazoline is prepared by reacting polyethylene polyamine with tall oil acids 250 C. to produce the aminoalkyl imidazoline. Other imidazolines are commercially available under the trade name Amine C, O and S and have the formula:

where R is principally undecyl (Amine C), heptadecenyl (Amine O) and he-ptadecenyl (Amine S) and the like.

The salts are simple to prepare and generally require admixing at from room temperature to about F. one mole of the alkyl or alkenyl succinic acid with an equivalent amount of amine preferably in a neutral hydrocarbon solvent such as isooctane, benzene or xylene and allowing the mixture to interact which normally requires from 2 to 10 hours. The solvent, if desired, can be removed by suitable means such as distillation.

The C alkyl and alkenyl succinic acids include octenyl, tetrapropenyl, heptadecenyl, octadecenyl, tetraisobutenyl, eicosenyl, heneicosyl, tricosenyl succinic acids.

For purpose of illustration, the following Example A is described:

One mole of Duomeen C was added while stirring to an equivalent amount of tetrapropenyl succinic acid in a xylene solvent at a rate slow enough to prevent a rise in temperature above 120 F. The reaction was stirred for 4-6 hours until the salt formation was complete after which the solvent was removed.

Other salts prepared by the method described include: (B) N-tetrapropenyl propylene diamine salt of heneicosyl succinic acid, (C) N-octadecenyl propylene diamine salt of heneicosyl succinic acid, (D) N-lauryl propylene diamine salt of tetrapropenyl succinic acid, (E) Noctyl diethylene triamine salt of heneicosyl succinic acid, (F) 1-hydroxyethyl-Z-heptadecenyl imidazoline salt of heneicosyl succinic acid, (G) 1-aminoethyl-Z-heptadecenyl imidazoline salt of tetrapropenyl succinic acid, (H) N-C alkenyl dipropylene triamine salt of octadecenyl succinic acid, (I) Duomeen T-salt of oleyl succinic acid, (J) Duomeen S salt of ricinoleyl succinic acid, (K) l-hydroxyethyl-Z-heptadecenyl imidazoline salt of tetrapropenyl succinic acid and mixtures thereof.

The base carrier to which the additive mixture of the present invention is incorporated in small amount in order Example I Percent weight Mixture of 90% of Ex. (A) salt and 10% tetrapropenyl succinic acid 0.001 Gasoline Balance Example II 1 Mixture of 90% Ex. (K) salt and tetrapropenyl succinic acid 0.001

Gasoline Balance Example 111 Mixture of 95% N-tetrapropenyl propylene diamine salt of henei'oosyl succinic acid and 5% 4 caps are then removed and 0.2 ml. of distilled water is placed in the dimple, the jars are recapped and are allowed to stand for five days (at 77i3 F.) the specimens are then examined for rust. The test is run in quadruplicate and at least three of the four specimens must be free of rust in order to pass the test.

Examples I and II passed the Chrysler Corrosion Test whereas similar compositions in which the free tetrapropenyl succinic acid was omitted (Ex. I and II) failed to pass this corrosion test.

Examples I to V were tested in the ASTM D-665-60 Synthetic Sea Water Rust Test (24 hours at 80 F.) and each of the Examples I-N passed the test whereas Example I to V (similar to Examples I-V but the free alkyl or alkenyl succinic acid was omitted) failed to pass the test.

Example III was tested in the Furnace Oil Rust Test which comprises visually examining for rust, steel panels treated with Example III composition for 16 hours and then exposing the steel panels to the same composition containing /2 weight percent water. The panels are rated qualitatively by estimating the fraction of area covered 1 Military specification JAN-H492.

of hene'icosyl succinic acid 0.005 with rust. Example III at even a lower concentration, Domestlc F1161 011 2 Balance 25 0.00l5%, allowed no rust whereas Domestic Fuel Oil Example IV No. 2 +0.0015% Santolene CP, a Ba phenol sulfonate, Mixture of 95% of N octoy1 diethylene triamine allowed 5% rust and Neat Fuel Oil No. 2 allowed 27% salt of heneicosyl snccinic acid and 5% of rustheneicosyl succinic acid 0.001 The following composltions were also tested under con- Mineral lubricating oil (SAE 10) Balance 30 ditions shown in Table I and the results were as follows:

TABLE I lBase; Diesel fuel] Humidity 1 BT-9 Humid" ASTM D-665 Additive percent weight Cabinet Life, ity 1 Corrosion Turbine Oil Rust Hrs. Lite, Hrs. Test, 48 Hrs.

VI 1.8% weight l-hydroxyethyl-zheptadecenyl 144+ 30 Pass, No rust.

imiiiazoline salt of tetrapropenyl succinic aci 0.2% weight Tetrapropenyl succinic acid l. VII..-" 1.8% weight N-Ci alkenyl propylene 144+ 30 D0.

diamine salt of tetrapropenyl succinic acid. 0.2% Weight Tetrepropenyl succinic acid X 1.8% weight l-aminoethyl-2-heptadecenyl 56 imidazoline salt of N -oleyl sarcosine. 0.2% weight Capric acid Y 2% weight 1-amin0ethy1-2-heptadecenylimid- 75 25 Moderate rust.

azoiine oi capric acid. Z Base incl 30 2 100% rust.

2 IHC Humidity Cabinet type test in which polished steel rods, predipped in test fluid, are maintained at 80 F. in a humid, 90 F. atmosphere [or 25 or more hours.

Example V Mixture of 90% of EX. G salt and 10% of heneicosyl succinic acid 0.002 Mineral lubricating oil (SAE 30) Balance cut in the form of an equilateral triangle 1% high with the corners turned down and a dimple of spherical radius in the center of the triangle. The specimens are-freshly polished with Armours 600A silicon carbide paper, cleaned wtih boiling benzene and boiled 1 minute in petroleum ether. They are then placed in 50 ml. of the test fuel in a 1%" diameter, 100 ml. wide-mount jar and allowed to stand at 77:3" F. for one hour. The jar Compositions of the present invention are also excellent vapor phase corrosion inhibitors protecting metals against corrosion for long periods of 6 months and more.

We claim as our invention:

l. A liquid hydrocarbon composition consisting essentially of a major amount of a liquid hydrocarbon and from about 0.001% to about 2% by weight of a mixture of (l) a C hydrocarbyl succinic acid, said hydrocarbon radical being selected from the group consisting of Cfl 3fi alkyl and C alkenyl radicals, and (2) a polyamine salt of a C hydrocarbyl succinic acid, the hydrocarbyl radical being the same as in the free acid compound, the polyamine being selected from the group consisting of N- tetrapropenyl propylene diamine, N-octyl diethylene triamine, N-C alkenyl propylene diamine, N-cocoanut propylene diamine, l-aminoethyl-2-heptadecenyl imidazoline and l-hydroxyethyl-2 heptadecenyl imidazoline; the free C alkenyl or alkyl succinic acid constituting from about 1% to about 20% of the additive mixture in the balance, 99% to being the polyamine salt.

2. A liquid hydrocarbon composition consisting essentially of a major amount of a liquid hydrocarbon and from about 0.000l% to about 2% by weight of a mixture of tetrapropenyl succinic acid and N-C alkenyl propylene diamine salt of tetrapropenyl succinic acid, the tetrapropenyl succinic acid constituting from about 1% to about of the additive mixture and the balance 99%-80% being the diamine salt.

3. A liquid hydrocarbon composition consisting essentially of a major amount of a liquid hydrocarbon and from about 0.0001% to about 2% by Weight of a mixture of tetrapropenyl succinic acid and N-aminoalkyl 2-heptadecenyl imidazoline salt of tetrapropenyl succinic acid, the tetrapropenyl succinic acid constituting from about 1% to about 20% of the additive mixture and the balance 99%- 80% being the imidazoline salt.

4. A liquid hydrocarbon composition consisting essentially of a major amount of a liquid hydrocarbon and from about 0.0001% to about 2% by weight of a mixture of tetrapropenyl succinic acid and N-hydroxyalkyl 2- heptadecenyl imidazoline salt of tetrapropenyl succinic acid, the tetrapropenyl succinic acid constituting from about 1% to about 20% of the additive mixture and the balance 99%80% being the imidazoline salt.

5. A gasoline composition consisting essentially of a major amount of gasoline and from about 0.0001% to about 2% by weight of a mixture of tetrapropenyl succinic acid and N-cocoanut propylene diamine salt of tetrapropenyl succinic acid the free acid constituting from about 1% to about 20% of the additive mixture and the balance 99%80% being the diamine salt.

6. A gasoline composition consisting essentially of a major amount of gasoline and from about 0.0001% to about 2% by Weight of a mixture of tetrapropenyl succinic acid and 1-hydroxyethyl-2-heptadecenyl imidazoline salt of tetrapropenyl succinic acid the free acid constituting from about 1% to about 20% of the additive mixture and the balance 99%80% being the imidazoline salt.

7. A liquid hydrocarbon fuel oil composition consisting essentially of a major amount of fuel oil and from about 0.0001% to about 2% by Weight of a mixture of tetrapropenyl succinic acid and N-cocoanut propylene diamine salt of tetrapropenyl succinic acid the free acid constituting from about 1% to about 20% of the additive mixture and the balance 99%-80% being the diamine salt.

8. A liquid hydrocarbon fuel oil consisting essentially of a major amount of fuel oil and from about 0.0001% to about 2% by weight of a mixture of tetrapropenyl succinic acid and 1-hydroxyethyl-2-heptadecenyl imidazoline 6 salt of tetrapropenyl succinic acid the free acid constituting from about 1% to about 20% of the additive mixture and the balance 99%-80% being the imidazoline salt.

9. A mineral lubricating oil composition consisting essentially of a major amount of mineral lubricating oil and from about 0.0001% to about 2% by weight of a mixture of tetrapropenyl succinic acid and N-cocoanut propylene diamine salt of tetrapropenyl succinic acid the free acid constituting from about 1% to about 20% of the additive mixture and the balance 99%80% being the diamine salt.

10. A mineral lubricating oil composition consisting essentially of a major amount of mineral lubricating oil and from about 0.000l% to about 2% by weight of mixture of a tetrapropenyl succinic acid and l-hydroxyet-hyl-Z-heptadecenyl imidazoline salt of tetrapropenyl succinic acid the free acid constituting from about 1% to about 20% of the additive mixture and the balance 99%80% being the imidazoline salt.

11. A liquid hydrocarbon fuel oil composition consisting essentially of a major amount of a liquid hydrocarbon fuel oil and containing about 0.001% of a mixture of of N-C alkyl diethylene triamine salt of tetrapropenyl succinic acid and 10% of tetrapropenyl succinic acid.

12. A liquid hydrocarbon fuel oil composition consisting essentially of a major amount of a liquid hydrocarbon fuel oil and containing about 0.0010.005% of a mixture of of N-tetrapropenyl propylene diamine salt of heneicosyl succinic acid and 5% of heneicosyl succinic acid.

References Cited by the Examiner UNITED STATES PATENTS 2,629,649 2/ 1953 Wachter 252'392 X 2,638,450 5/1953 White 44-71 X 2,779,740 1/1957 Messina 252-515 3,216,396 11/1965 Le Suer 4471 3,219,666 11 /1965 Norman et al. 252-51.5 XR

FOREIGN PATENTS 601,931 7/1960 Canada.

DANIEL E. WYMAN, Primary Examiner.

C. O. THOMAS, Y. M. HARRIS, Y. H. SMITH,

Assistant Examiners.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2629649 *Oct 31, 1949Feb 24, 1953Shell DevVapor-phase corrosion inhibitor
US2638450 *Jan 17, 1950May 12, 1953Socony Vacuum Oil Co IncReaction products of nu-alkylated polyalkylenepolyamines and alkenyl succinic acid anhydrides
US2779740 *Nov 25, 1953Jan 29, 1957Tidewater Oil CompanyMineral oil lubricating compositions
US3216396 *Aug 10, 1964Nov 9, 1965Scamman William HPig farrowing house
US3219666 *Jul 21, 1961Nov 23, 1965 Derivatives of succinic acids and nitrogen compounds
CA601931A *Jul 19, 1960Standard Oil CoStabilization of fuel oil compositions
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3447918 *Oct 26, 1967Jun 3, 1969Standard Oil CoRust inhibitors
US3493354 *Feb 27, 1967Feb 3, 1970Monsanto ChemicalsDiesel fuel additive
US3527583 *Apr 25, 1966Sep 8, 1970Gulf Research Development CoMotor fuel multipurpose agents
US3527584 *Apr 25, 1966Sep 8, 1970Gulf Research Development CoMotor fuel multipurpose agents
US3615291 *Aug 29, 1969Oct 26, 1971Gulf Research Development CoEthoxylated or propoxylated 1,2,4- or 1,2,5-trisubstituted imidazolines and lecithin mixtures and reaction products thereof
US4737159 *Jun 29, 1984Apr 12, 1988E. I. Du Pont De Nemours And CompanyCorrosion inhibitor for liquid fuels
US5599779 *Mar 20, 1996Feb 4, 1997R. T. Vanderbilt Company, Inc.Synergistic rust inhibitors and lubricating compositions
US6043199 *Nov 13, 1998Mar 28, 2000Exxon Research And Engineering Co.Corrosion inhibiting additive combination for turbine oils
US8575237Jun 19, 2013Nov 5, 2013Jacam Chemical Company 2013, LlcCorrosion inhibitor systems using environmentally friendly green solvents
EP0899324A1 *Aug 25, 1998Mar 3, 1999Exxon Research And Engineering CompanyCorrosion inhibiting additive combination for turbine oils
WO2010042378A1 *Oct 1, 2009Apr 15, 2010The Lubrizol CorporationAdditives to reduce metal pick-up in fuels
Classifications
U.S. Classification508/283, 252/392, 252/396, 44/403, 508/511
International ClassificationC10L1/22, C10L1/14, C10L1/18
Cooperative ClassificationC10M2215/04, C10M2207/123, C10L1/1883, C10L1/2383, C10M2207/22, C10M2215/26, C10L1/2225, C10L1/232, C10L1/2222, C10M2227/082, C10M2215/224, C10L1/143, C10M1/08, C10M2207/129
European ClassificationC10L1/14B, C10M1/08