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Publication numberUS3649229 A
Publication typeGrant
Publication dateMar 14, 1972
Filing dateDec 17, 1969
Priority dateDec 17, 1969
Publication numberUS 3649229 A, US 3649229A, US-A-3649229, US3649229 A, US3649229A
InventorsOtto Ferdinand P
Original AssigneeMobil Oil Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Liquid hydrocarbon fuels containing high molecular weight mannich bases
US 3649229 A
Abstract
Reaction products obtained from high molecular weight alkyl-substituted hydroxyaromatic compounds, amines and aldehydes are detergency improvers for liquid hydrocarbon fuels.
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Description  (OCR text may contain errors)

United States Patent Otto Mar. 14, 1972 [54] LIQUID HYDROCARBON FUELS 2,459,112 1/1949 Oberright ..252/51.5 R CONTAINING HIGH MOLECULAR 2,684,293 7/1954 Hill et al. 44/73 X WEIGHT MANNICH BASES 2,962,442 11/1960 Andress..... 44/73 X 2,984,550 5/1961 Chamot ..44/73 X [72] Inventor: Ferdinand P. Otto, woodbury, NJ. 3,368,972 2/1968 Otto ..252/5l.5 R

3,413,347 11/1968 Worrell ..252/5l.5 R [73] Ass'gnee' Cwpmm 3,416,903 12/1968 Eckert et a1. ..44/73 [22] Filed: Dec. 17, 1969 Primary ExaminerDaniel E. Wyman [21] APPLNO" 885995 AssistantExaminer-W. J. Shine Attorney-Oswald G. Hayes, Andrew L. Gaboriault, Raymond [52] U.S. Cl ..44/73, 252/392 W. Barclay and Claude E. Setliff [51] Int. Cl. ..Cl011/22 [58] Field of Search ..44/73; 233/392 [57] ABSTRACT Reaction products obtained from high molecular weight alkyl- [56] References cued substituted hydroxyaromatic compounds, amines and a1- UNITED STATES PATENTS dehydes are detergency improvers for liquid hydrocarbon fuels. 2,348,638 5/1944 Mikeska et a1 ..44/73 X 2,364,502 12/ 1944 Zimmer et al ..44/73 X 10 Claims, N0 Drawings LIQUID HYDROCARBON FUELS CONTAINING HIGH MOLECULAR WEIGHT MANNICH BASES BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to liquid hydrocarbon combustion fuels. More particularly, the invention relates to liquid hydrocarbon combustion fuels having detergency properties imparted thereto by incorporating therein a reaction product of the Mannich base type made by using a high molecular weight alkyl-substituted hydroxyaromatic compound.

2. Discussion Of The Prior Art It is well known to those in this art that liquid hydrocarbon combustion fuels, such as fuel oils and gasolines, tend to exhibit certain deleterious characteristics, either after long periods of storage or under actual operational conditions. Gasolines, for example, in operational use tend to deposit sludge and varnish at various points in the power system, including carburetor and intake valves. It is desirable, therefore to find a means for improving liquid hydrocarbon fuels by lessening their tendancy to leave such deposits.

US. Pat. No. 3,368,972 discloses the use of Mannich base products in lubricating oils as detergency agents. However, there is no teaching therein or suggestion therefrom that such products can be used in fuels.

SUMMARY OF THE INVENTION In accordance with this invention, there is provided a liquid hydrocarbon combustion fuel containing an amount sufficient to impart improved detergency and antirust properties thereto of an additive composition comprising the condensation product of (l a high molecular weight alkyl-substituted hydroxy-aromatic compound wherein said alkyl has a molecular weight of from about 600 to about 3,000, (2) an amine, which contains an HN group and (3) an aldehyde, wherein the respective molar ratio of reactants is l:0.l-l:0. 1 -l0.

DESCRIPTION OF SPECIFIC EMBODIMENTS In general aspect, the additive compositions utilizable in this invention may be made from (I) a high molecular weight alkyl-substituted phenol, wherein the alkyl substituent has a molecular weight of from about 600 to about 3,000, preferably from about 750 to about 1,200, (2) an aldehyde and (3) an amine which contains an I-IN group, i.e'., an active hydrogen, wherein the respective molar ratio of reactants is as already stated.

The reaction involved in preparing the high molecular weight phenol may be depicted as follows:

(OH) x (OH) x (R)? IR (RI) 1 wherein R is a hydrocarbon or substituted hydrocarbon radical, R is a polyalkylene compound wherein the repeating alkyl unit may be from C to C x is an integer from 1 to 2, y is an integer from 0 to 2 and z is an integer from 1 to 2. Use of this product to form the Mannich bases will become apparent from the Examples set forth hereinafter.

Representative high molecular weight alkyl substituted phenols contemplated by the present invention are polypropylphenol, polybutylphenol, polyamylphenol and similarly substituted phenols. For example, in place of phenol, high molecular weight alkyl substituted compounds of resorcinol, hydroquinone, catechol, eresol, xylenol, amyl phenol, hydroxydiphenyl, benzylphenol, phenylethylphenol, phenol resins, methylhydroxydiphenyl, guiaeol, alpha and beta naphthol, alpha and beta methylnaphthol, tolylnaphthol, xylylnaphthol, benzylnaphthol, anthranol, phenylmethylnaphthol, phenanthrol, monemethyl ether and catechol, phenoxyphenol, chlorophenol, hydroxyphenyl sulfides and the like may be used.

Aldehydes contemplated by the present invention are the aliphatic aldehydes, typified by formaldehyde (such as trioxymethylene) aeetaldehyde, and aldol (B-hydroxy butyraldehyde); aromatic aldehydes, representative of which is benzaldehyde; heterocyelic aldehydes, such as furfural; etc. The aldehyde may contain a substituent group such as hydroxyl, halogen, nitro and the like; in short, any substituent which does not take a major part in the reaction. Preference, however, is given to the aliphatic aldehydes, formaldehyde being particularly preferred.

The amines contemplated herein are those which contain an amino group characterized by the presence of at least one active hydrogen atom. Such amines may contain only primary amino groups, only secondary amino groups, or both primary and secondary groups. Typical amines are the polyalkylpolyamines, ethylenediamine, propylenediamine, polyalkene polyamines (e.g., diethylene triamine, triethylene tetramine); the aromatic amines 0-, mand p-phenylene diamine, diamino naphthalenes; the acid substituted polyalkylpolyamines, N- acctyl tetraethylenepentamine, and the corresponding formylpropionyl-, butyryl-, and the like N-substituted compounds; and the corresponding eyelized compounds formed therefrom, such as the N-alkyl amines of imidazolidine and pyrimidine. Secondary heterocyclic amines which are suitable are those characterized by attachment of a hydrogen atom to a nitrogen atom in the heterocyclic group. Representative of the amines contemplated herein are morpholine, thiomorpholine, pyrrole, pyrroline, pyrrolidine, indole, pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine, piperidine, phenoxazine, phenthiazine and their substituted analogs. Substituent groups attached to the carbon atoms of these amines are typified by alkyl, aryl, alkaryl, aralkyl, cycloalkyl, and amino compounds referred to above.

It is also contemplated that the term amine" shall include the product obtained by reacting an alkenyl succinic anhydride of the formula or alkenyl suecinic acid of the formula with the amines of the foregoing paragraph. See US. Pat. No. 3,346,493.

In the above formulae, R is an alkylene group. The alkenyl radical can be straight-chain or branched-chain; and it can be saturated at the point of unsaturation by the addition of a substance which adds to olefinic double bonds, such as hydrogen, sulfur, bromine, chlorine, or iodine. It is obvious, of course, that there must be at least two carbon atoms in the alkenyl radical, but there is no real upper limit to the number of carbon atoms therein, The alkenyl succinic acid anhydrides and the alkenyl succinic acids are interchangeable for the purposes of the present invention. Accordingly, when the term alkenyl suecinic acid anhydride is used herein, it must be clearly understood that it embraces the alkenyl suceinie acids as well as their anhydrides, and the derivatives thereof in which the olefinic double bond has been saturated, as set forth hereinbefore. Nonlimiting examples of the alkenyl succinic acid anhydride component are ethenyl succinic acid anhydride; ethenyl suecinie acid; ethyl suceinie acid anhydride; propenyl succinic acid anhydride; sulfurized propenyl succinic acid anhydride; butenyl succinic acid; 2-methylbutenyl suceinic acid anhydride; 1,2-dichloropentyl suceinic acid anhydride; hexenyl succinic acid anhydride; hexyl succinic acid; sulfurized 3-methylpentyl succinic acid anhydride; 2,3-

tiimethylbutenyl succinic acid anhydride; 3.3-dimethylbutenyl iUCCllllC acid; l.2-dibromo-2-ethylbutyl SUCCll'llC acid; heptenyl succmic acid anhydride; l...-diiodooctyl succinic acid; octenyl succinic acid anhydride; diisobutenyl succmic acid anlhydride; .Z-methylheptenyl succmic acid anhydride; 4-ethylliexenyl succinic acid; l-isopropylphentenyl succmic acid anlnydride; nonenyl succinic acid anhydride'. I-propylhexenyl IiUCClnlC acid anhydride; decenyl succinic acid: decenyl suciainic acid anhydride'. S-methyl-2-isopropyl-hexenyl succmic .icid anhydride; l.2-dibromo-Z-ethyloctenyl succinic acid anliydride; decyl succinic acid anhydride; undecenyl succinic acid anhydride; 1.2-dichloroundecyl succinic acid; 3-ethyl-2- t-butylpentenyl succinic acid anhydride: tetrapropenyl suci.:inic acid anhydride'. tetrapropenyl succinic acid; triisobutenyl succinic acid anhydride'. Z-propyl-noneyl succinic acid anliydride; 3-butyloctenyl succinic acid anhydride; tridecenyl :succinic acid anhydride'. tetradecenyl succinic acid anhydride; lhexadecenyl succinic acid anhydride; sulfurized octadecenyl iiuccinic acid; octadecyl succinic acid anhydride; l.2- dibromo-Z-meihylpentadecenyl succmic acid anhydride; 8- propylpentadecyl,succinic acid anhydride; eicosenyl succmic acid anhydride; l.2-dichloroZ-methylnonadecenyl succinic acid anhydride; E-octyldodecenyl SUCClDlC acid; [.2- iiliiodotetracosenyl succinic acid anhydride; hexacosenyl suctZlnlC acid; hexacosenyl succmic acid anhydride; and hentriacontenyl succinic acid anhydride. In general. alkenyl suci.:inic acid anhydrides having from about eight to about 35. and preferably. from about nine to about 18 carbon atoms in the alkenyl group thereof. are most advantageously employed in the novel additive compositions. Methods for preparing the alkenyl succinic acid anhydrides are well known to those Familiar with the art. the most feasible method comprising the reaction of an olefin with maleic acid anhvdride. more .letailed description of the alkenyl succinic acid anhydrides iuitable for use in the additive compositions of the present iniention and their preparation. is disclosed in [1.5. Pat. No. 2.638.450. issued May 12..953.

The polyalkyl phenols of this invention may be made by reacting 0.1 to moles of a phenol with l mole of a polyalkylene in the presence of an alkylating catalyst. such as Bl} i including the etherate. phenolate or phosphate complexes), BF or HCl gas. AlCl at 80 to 250 C. This process is particuiarly effective when conducted by reacting l to 1.5. or especially 1.25 moles. of phenol to l mole of a polyalkylene compound in the presence of a BF phenolate at about l50 C. The product is conveniently dissolved in an aromatic solvent and then washed with water to remove unreacted components. Upon filtration and removal of the aromatic solvent bv distilla- H011. the product. a clear. viscous oil. remains.

The preparation of the high molecular weight alkyl-sub- :itituted phenols used in this invention may be illustrated by the preparation of polypropylphenol from phenol and polypropylene with a BF 2C H OH-catalyst. For example. the following was charged into a SO-gallon glass-lined Pfaudler iltettle:

.34 kg. (42.5 moles) polypropylene (M.W.=800) .5 kg. (42.5 moles percent excess) phenol 13.25 kg. BF 2C H OH 26 percent BF (585 g. BF

The mixture was heated and stirred for 4 hours at 300 F.. then it was cooled down to [75 F. and 14 kg. toluene. 3.4 kg. butyl alcohol and 34 kg. distilled water were added to wash but the Bland the unreacted phenol. After that. the mixture in the kettle was washed with 5 percent aqueous KOl-l solution to remove any remaining phenol. then with 5 percent aqueous KCL solution to neutralize the unreacted KOH and finally three times with distilled water until neutral to litmus at a temperature in the vicinity of 150 F.

The washed mixture was filtered through a Sparkler ii-lorizontal plate filter using pound of Hyflo filter aid tdiatomaceous earth) and then the toluene and butyl alcohol were stripped off under vacuum (-40 mm.) at 300 F. The product. a clear. brown. viscous oil. gave the following analysis;

active hydrogen (Zerevitinov determination);

lieory nmoles Ch /g. l Hound iilo. 0.85

tield based on the active H analysis= 76.5%.

Ihromatographic clay separation 73.5% yield.

"he high molecular weight alkyl-substituted phenol used in his invention may be prepared by any other suitable means.

"The additive composition. i.e.. the aforementioned reaction product. is added to the fuel in a small amount to attain the objects hereinbefore discussed. In general. the additive com- TJOSlIlOl'l may vary from about 1 to about 200. and. preferably. from about 1 to about 25. pounds per thousand barrels of fuel; )r. in corresponding terms of percent. by weight. the concen tration of additive composition may vary from about 0.00025 :0 about 0.l. and preferably. from about 0.00025 to about 3.01 percent. by weight. ot'the fuel.

he following examples and comparative data are intended :0 illustrate the novel additive compositions of the present invention and to demonstrate their effectiveness in improving "he properties of liquid hydrocarbon combustion fuels. It will 5e understood. of course. that it is not intended the invention we limited to the particular compositions shown or to the ioerations or manipulations involved. Various other additive compositions. and other fuels. can be utilized. as those skilled .n the art will readily appreciate.

EXAMPLE l This example illustrates the Mannich reaction of polypropylphenol with dimethylamine and formaldehyde. The "ollowing reactants were employed:

"nlvpropyl henol lM.W 000.

The apparatus consisted of a l-liter. four-necked reaction flask equipped with a mechanical stirrer. reflux condenser. thermometer. dropping funnel and later. a nitrogen inlet tube.

The polypropylphenol with the mineral oil and .iimethylamine were charged to the flask at a temperature of 30 C. and the solution of formaldehyde was added dropwise through the dropping funnel with continuous stirring. After one hour. the temperature was raised to C. and held there for 3 hours while the dropping funnel was replaced by an .nlet tube and nitrogen gas was passed through. The mixture. after adding 100 cc. toluene and 50 cc. butyl alcohol. was washed three times with hot water until neutral to litmus to remove the unreacted amine and formaldehyde. The solution was filtered and stripped under vacuum (5-10 mm.) in a nitrogen atmosphere to 200 C. The product was a clear. orange oil with the following analysis:

Theory: active hydrogen. 0.41 mmoles CH /g.; oxygen, 0.89%; total nitrogen. 0.55%; basic nitrogen. 0.55%. Found: active hydrogen. 0.35 mmoles CH /g.; oxygen, 0.68%; total nitrogen. 0.45%; basic nitrogen. 0.47%.

I EXAMPLE 2 This example illustrates the Mannich reaction of polypropylphenol with dimethylaminopropylamine and formaldehyde. The following reactants were employed:

Polypropylphenol (M.W. 900,

active H'=0.85) 50 g. Mineral oil 50 g. Dimethylaminopropylamine (M.W. I02) l2 g. 37% aqueous formaldehyde 50 g. Xylene l50 cc.

/CH; l CHZO HZNCHZCHgCH N OH A CHzNHCH CHgCHgN H2O The apparatus consisted of a 500 ml. four-necked reaction flask equipped with a mechanical stirrer, reflux condenser, thermometer, dropping funnel and later, a nitrogen inlet tube.

The polypropylphenol with the mineral oil and dimethylaminopropylamine were charged to the flask at room temperature and the solution of formaldehyde was added dropwise through the dropping funnel during a half hour period with continuous stirring. A cloudy mixture was formed, the temperature rose to 50 C. and 150 cc. xylene was added while the dropping funnel was replaced by an inlet tube and nitrogen gas was passed through. The mixture was refluxed for 3 hours and after cooling down was washed with hot water to remove the unreacted amine until neutral to litmus. Then the xylene was stripped off under vacuum (5-10 mm.) at 200 C. The product, a clear, light brown oil gave the following analysis:

Theory: total nitrogen, 1.08%; basic nitrogen, 1.08%. Found: total nitrogen, 0.91%; basic nitrogen, 0.89%.

EXAMPLE 3 This example illustrates the Mannich reaction of polypropylphenol with tetraethylenepentamine and paraformaldehyde (ratio 2:1:2). The following reactants were employed:

Poiypropylphenol (M.W. 900,

act. H'=0.85) 2,200 g. Tetraethylenepentamine 187 g. Pural'ormaldehyde 59.4 g.

The apparatus consisted of a 5-liter, four-necked reaction flask equipped with a mechanical stirrer, reflux condenser with a Dean-Stark water takeoff, thermometer, dropping funnel and later, a nitrogen inlet tube.

The polypropylphenol and paraformaldehyde were charged to the flask at a temperature of 70 C. and the tetraethylenepentamine was added dropwise through the dropping funnel with stirring. The reaction mixture was stirred and heated to C. in the presence of nitrogen and held at this temperature for 4 hours. During this time, 34 cc. water was evolved (theory 36 cc.). The product was filtered hot by suction through an electrically heated Buchner funnel containing a layer of Hyflo clay (a diatomaceous clay filter aid).

The filtrate was a clear, brown, viscous oil with the following analysis:

Percent theory: total nitrogen, 2.86; basic nitrogen, 2.86. Percent found: total nitrogen, 2.61; basic nitrogen, 2.31.

EXAMPLE 4 This example illustrates the Mannich reaction of polybutylphenol with tetraethylenepentamine and paraformaldehyde (ratio 2: l :2). The following reactants were employed:

Tetraethylenepentamine 15 g. Paral'ormaldehyde 5 g. Polybutylphenol (M.W.= i000) 200 g.

The same procedure was followed as in Example 3. The final product was a clear, brown, viscous oil with the following analysis:

Percent theory: total nitrogen, 2.50; basic nitrogen, 2.50. Percent found: total nitrogen, 2.42; basic nitrogen, 1.90.

EXAMPLE 5 This example illustrates the Mannich reaction of polypropylphenol with N-acetyl-tetraethylenepentamine and paraforrnaldehyde (ratio 2:1:2). The following reactants were employed:

Polypropylphenol (M.W. 900,

act. H=0.85) 2,000 g. N-acetyl-tetraethylenepentamine 196 g. Paraformaldehyde 50 g,

The apparatus consisted of a 5-liter, four-necked reaction flask equipped with a mechanical stirrer, reflux condenser with a Dean-Stark water takeoff, thermometer and later, a nitrogen inlet tube.

The polypropylphenol and N-acetyl-tetraethylenepentamine were charged to the flask at a temperature of 60 C. and the paraformaldehyde was added slowly in a period of A hour. The reaction mixture was heated and stirred in the presence of nitrogen to 200 C. and held at this temperature for 4 hours. During this time, 30 cc. water was evolved (theory 30 cc.). The product was filtered hot by suction through an electrically heated Buchner funnel containing a layer of Hyflo clay, and a clear, brown viscous oil was obtained with the following analysis:

Percent theory: total nitrogen, 2.30; basic nitrogen, 1.84. Percent found: total nitrogen, 2,43; basic nitrogen, 1.70.

EXAMPLE6 This example illustrates the Mannich reaction of polypropylphenol with diethylenetriamine and paraformaldehyde (ratio 110.75: 1 The following reactants were employed:

Polypropylphenol (M.W. 900,

act. H=0.85) 2,200 g. Diethylenetriamine 144.43 g. Paraformaldehyde 55 g.

The apparatus consisted of a -liter. four-necked reaction flask equipped with a mechanical stirrer. thermometer. reflux condenser and later a Dean-Stark water takeoff was added to the condenser. The polypropylphenol and diethylenetriamine were charged to the flask at a temperature of 60 C. and the paraformaldehyde was added slowly over a period of 50 minutes. The reaction mixture was stirred and heated to 120 C. and held there for 2 hours. At this point. a Dean-Stark water takeoff was added. nitrogen gas was introduced and the temperature raised to 150 C. and held there for 2 /2 hours. During this time. 30 cc. water was evolved (theory 30 cc.). The mixture was stripped under vacuum (5-10 mm.) for 1 hour at 150 C. and 50 g. unreacted amine was recovered. The product was a clear. brown viscous oil which gave the followung analysis:

Percent theory: total nitrogen, 1.62; basic nitrogen. 1.62.

Percent found: total nitrogen. 1.65; basic nitrogen. 1.60.

EXAMPLE? This example illustrates the Mannich reaction of polypropylphenol sulfide with diethylenetriamine and paraformaldehyde. The following reactants were employed:

Polypropylphcnol sulfide (50% Promor The apparatus was the same as in Example 6. The polypropylphenol sulfide mixture (50% Promor No. 5) and diethylenetriamine were charged to the flask at room temperature and the paraformaldehyde was added slowly over a period of minutes. The reaction mixture was stirred and heated to 180 C. for 3% hours. The mixture in the flask was stripped under vacuum (5-l0mm.) at I80 C. and some unreacted amine was recovered. The product. a dark brown oil gave the following analysis:

Percent theory: Total nitrogen, 0.77

Percent found: Total nitrogen, 0.69

EXAMPLE 8 The example illustrates the Mannich reaction of wax phenol, where the wax has an average of about 24 carbon atoms, with diethylenetrlamlneand para formaldehyde (ratio :0.75:1 The following reactants were employed:

.1-14) Wax phenol Z6l g. liethyleneinamine (M.W 103) 25.5 g. "maformuldehyde (MAN 10) 10 g. romor Oil No. 5 (for 509; all dilution) 290 g.

The setup consisted of a 2-liter, four-necked reaction flask with a mechanical stirrer, thermometer and condenser The wax-phenol, Promor Oil No. 5 and diethylenetriamine were charged to the flask at a temperature of about 50 C., and the paraformaldehyde was added slowly in a period of 1 hour. The reaction mixture was refluxed for 1 hour. Nitrogen gas was introduced and the water was removed at a temperature of l30-l50 C. in a period of 1V2 hours. Then vacuum was applied (10 mm. Hg) for 1% hours at 150 C. After filtratron, a brown oil was obtained which had the following analyits:

Percent found: Total nitrogen, 1.82.

EXAMPLE 9 This example illustrates the Mannich reaction of ,polypropylphenol with diethylenetriamine and paraformaldehyde (ratio l:0.6:2). The following reactants were em- :Jloyed:

olvpropylphenol (M.W. 825.

lct. Hfll75) 4000 g. Jiethylenetriamine (M.W. 103) 185 g. Paral'ormaldehyde 180 g. romor Oil No. S (for 25 1' oil dilution) i433 g.

The setup consisted ofa l2-liter, four-necked reaction flask equipped with a mechanical stirrer, condenser, thermometer mo a nitrogen inlet tube.

The mixture of polypropylphenol, diethylenetriamine and Promor Oil No. 5 were charged in the flask and paraformaldehyde was added slowly in a period of 3 hours at a temperature of 70-90 C. The mixture was refluxed for 2 hours and :he water was removed with nitrogen gas at a temperature of 00-l50 C. in 1 hour. Then vacuum was applied (5 mm. Hg) r'or 2 hours at 150 C. and a clear, brown viscous oil was obamed containing 25 oil which gave the following analysis:

Percent theory: total nitrogen, [.30. Percent found: total nitrogen, 1.30.

EXAMPLE l0 This example illustrates the preparation of monosuccinimide of dodecenyl-succinic anhydride with diethylenetriamine. The following reactants were employed:

.Jodecenyl-succmic anhydride (2 moles) MW. 266) 533 g. Diethylenetriamine (2 moles +10% excess) M.W. 103) 227 llylene 400 g.

The setup consisted ofa 3-liter, four-necked reaction flask equipped with a mechanical stirrer, reflux condenser with a Dean-Stark water takeoff, thermometer, dropping funnel and later a nitrogen inlet tube.

The diethylenetriamine and xylene were charged into the flask and dodecenyl-succinic anhydride was added dropwise in 2 hours at a temperature from 50 C. up to C. Water was removed by refluxing with nitrogen gas for 1% hours at C. (about 55 cc.) and then the mixture was stripped under vacuum (5 mm. Hg) for 1% hours at 150 C. to remove the unreacted amine. A clear, very viscous product was obtained with the following analysis:

Percent theory: total nitrogen, 11.5. Percent found: total nitrogen, 10.56.

EXAMPLE 1 1 This example illustrates the Mannich reaction of (ratio 1:1 1.5). The following reactants were employed:

Polypropylphenol (active H=0.8) 1500 g. Dodecenybsuccinimitle-diethylenetriamine (Ex. 462 g. Paral'ormaldehyde 54 g. Promor Oil No.5 ((012257: oil dilution) 660 g..

The setup consisted of a 5 -lit efifour-necked flask with a mechanical stirrer, thermometer, nitrogen inlet tube and condenser.

The polypropylphenol, dodecenyl-succinimide and Promor Oil No. 5 were charged in the flask and paraformaldehyde was added slowly in a period of 2% hours at a temperature of 8090 C., then the water was removed with nitrogen gas at first under light vacuum and then the mixture was stripped under 5-10 mm. Hg. vacuum for 3 hours at 150 C. A total of 23 cc. water was removed (theory 22 cc. water). The final product was a clear, viscous oil containing 25% Promor No. 5which gave the following analysis:

Percent theory: nitrogen, 1.85. Percent found: nitrogen, 1.77.

EXAMPLE 12 This example illustrates the Mannich reaction of polypropylphenol with diethylenetriamine and paraformaldehyde (ratio 1:0.612) (similar to Example 9 but higher molecular weight polypropylphenol was used). The following reactants were employed:

Polypropylphenol (polypropylene M.W.

I120. active H=0.76) 2000 g. Diethylenetriamine (M.W. 103) 93.8 g. Parat'ormaldehyde 91.8 g. Promor Oil No. 5 (for 2571 oil dilution) 712.0 g.

Percent found: total nitrogen, l .49.

The additive compositions of the present invention impart valuable properties, as hereinbefore indicated, to liquid hydrocarbon combustion fuels, including the distillate fuels, i.e., gasolines and fuel oils. Accordingly, the fuel oils that may be improved in accordance with the present 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 restricted 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.

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 D396-48T. Specifications for diesel fuels are defined in A.S.T.M. Specification D975-48T. Typical jet fuels are defined in Military Specification MlL-F-5624B.

The gasolines that are improved by the additive compositions of this invention, are mixtures of hydrocarbons having an initial boiling point falling between about F. and about F. and an end-boiling point falling between about 250 F. and about 450 F. As is well known in the art, motor gasoline can be straight run gasoline or, as is more usual, it can be a blend of two or more cuts of materials including straight run stock, catalytic or thermal reformate, cracked stock, alkylated natural gasoline, and aromatic hydrocarbons. 7

The utility of the Mannich products of this invention as additives for fuels has been shown by a number of comparative tests conducted on the fuel alone and on the fuel blended with minor amounts of the Mannich products described in the preceding examples. Both bench tests and engine tests were employed. Carburetor Detergency Test The deposit-forming tendencies of a fuel are determined in an 8-hour engine test. This accelerated test, when run on fuels that contain no detergents, produces an amount of deposit equivalent to the amount observed in 4,000 miles of operation in field tests on taxicab fleets. A six-cylinder Chevrolet engine is equipped with notched rings to increase the amount of flowby and with a glass throttle body section. The engine is operated for 8 hours, using the fuel under test, at alternate idling and running cycles. In the idle cycle, the engine is run at idling speed of 400 rpm. with no load, for 5 minutes. Then for 1 minute, the engine is run at a speed of 2,500 rpm. under a load of 30 BPI-I and at 9.4 in. of mercury manifold pressure. During the running cycle, the blowby and part of the exhaust are released into the carburetor air intake during the idling cycle. After 8 hours operation at alternate run and idle, the carburetor is examined and rated as to the amount of deposit in the throttle throat. In the rating scale, a rating of 0 (zero) indicates a clean carburetor; l--trace deposits; 2=light deposits; 3=medium deposits; and 4=heavy deposits.

CARBURETOR DETERGENCY TEST IN GASOLINE [Inhibitors blended in a fuel comprising 40% TCC gasoline, 40% reformate and 20% light alkylate approximately 85-415 F.

boiling range. 3 cc./gallon offuel of tetraethyllead is present] these contain same nitrogen content ditto Rust Test In Gasoline The rusting characteristics of gasoline were determined in a Static Rust Test, which simulates conditions encountered in storage vessels. The gasoline used was the same as that used in the Carburetor Detergency Test. The test used was ASTM D- 665 except that the temperature was 80 F. instead of F. and the time was 48 hours instead of 24 hours.

The results of this test were as follows.

MODIFIED ASTM RUST TEST D-665 The unhibited gasoline had a rating of 80% rusting in both specimens.

While the present invention has been described with illustrative embodiments. it should be understood that modificalions and variations may be resorted to without departing from the spirit and scope of the invention as will be understood by those skilled in this art.

lclaim:

l. A liquid hydrocarbon combustion fuel containing an amount sufficient to impart improved detergency properties thereto of an additive composition comprising the condensation product of l a high molecular weight sulfur free alkylsubstituted hydroxyaromatic compound wherein the alkyl has ti molecular weight of from about 600 to about 3.000. (2) an amine which contains an amino group having at least one active hydrogen atom and (3) an aldehyde wherein the respective molar ratio of reactants is 1:0. ll0:0.1 -10.

2. The liquid hydrocarbon combustion fuel of claim 1 wherein the said condensation product comprises from 1 to about 200 pounds per thousand barrels offuel.

i. The liquid hydrocarbon combustion fuel of claim 1 will) iii lib

wherein the said condensatidrfiart iFct comprises from 1 to mom 25 pounds per thousand barrels of fuel.

ll, The liquid hydrocarbon combustion fuel of claim 1 wherein the molecular weight of the alkyl substituent is from about 750 to about [200.

5. The liquid hydrocarbon combustion fuel of claim 1 vnerein the alkyl-substituted hydroxyaromatic compound is in alkyl-substituted phenol.

ti. The liquid hydrocarbon combustion fuel of claim 1 wherein said aldehyde is selected from the group consisting of T'ormaldehyde and paraformaldehyde.

l. The liquid hydrocarbon combustion fuel of claim 1 wherein said amine is selected from the group consisting of polyalkylpolyamines. polyalkenylpolyamines, aromatic amines carboxylic acid-substituted polyalkylpolyamines, and the succinimide formed from any one of these with an olefinic iuccinic acid or anhydride.

8. The liquid hydrocarbon combustion fuel of claim 1 wherein said amine is selected from the group consisting of iiimethylamine. dimethylaminopropylamine, tetraethylenepentamine, N-acetyl-tetraethylenepentamine, diethylenetriamine and the monosuccinimide prepared from clodecenyl succinic anhydride and diethylenetriamine.

9. The liquid hydrocarbon combustion fuel of claim 1 wherein said alkyl-substituted hydroxyaromatic compound is selected from the group consisting of polypropyl phenol and polybutyl phenol.

10. The liquid hydrocarbon combustion fuel of claim I wherein said alkyl-substituted hydroxyaromatic compound is polypropyl phenol from polypropylene having a molecular weight of 825, said amine is diethylenetriamine, and said aldehyde is paraformaldehyde and the said respective molar Notice of Adverse Decision in Interference 0 Patent No. 3,6L9,229, F. P. Otto,

In Interference No. 98,623 invoivin LIQUID HYDROCARBON FUELS CONTAINING HIGH MOLECU- LAR \VEIGHT MANNICH BASES, final judgment adverse to the patentee Oct. 6, 1975, as to claims 1, 2, 3, 4:, 5, 6, 7, 8 and 9.

was rendered [Ofi'im'al Gazette Febmm'y 10, 1976.]

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Classifications
U.S. Classification44/347, 252/392, 44/424, 44/425
International ClassificationC10L1/10, C10L1/22
Cooperative ClassificationC10L1/221
European ClassificationC10L1/22W