Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.


  1. Advanced Patent Search
Publication numberUS3849083 A
Publication typeGrant
Publication dateNov 19, 1974
Filing dateApr 14, 1972
Priority dateApr 14, 1972
Publication numberUS 3849083 A, US 3849083A, US-A-3849083, US3849083 A, US3849083A
InventorsM Dubeck
Original AssigneeEthyl Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Gasoline additive
US 3849083 A
Gasoline containing ether amines as carburetor detergents; and ether amine additive concentrates.
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent [191 Dubeck Nov, 19, 1974 [52] US. Cl. 44/72 [51] Int. Cl Cl0l l/22 [58] Field of Search 44/72 [56] References Cited UNITED STATES PATENTS 3.478,096 11/1969 Cyba 44/74 3,637,358 l/l972 Cyba 252/403 Primary ExaminerPatrick P. Garvin Assistant Examiner-Mrs. Y. H. Smith Attorney, Agent, or Firm-Donald L. Johnson; Robert A. Linn [5 7 ABSTRACT Gasoline containing ether amines as carburetor detergents; and ether amine additive concentrates.

7 Claims, No Drawings GASOLINE ADDITIVE BACKGROUND OF THE INVENTION The invention involves the use of certain ether amines as carburetor detergents.

Deposits which form on various internal parts of internal combustion engine carburetors are undesirable. These deposits tend to reduce the efficiency of the carburetor and ultimately the performance of the engine itself. Gasoline additives which reduce or remove these undesirable deposits are available. These additives are commonly referred to as carburetor detergents.

Ether amines having the formula where R is sec-alkyl or cycloalkyl, R is hydrogen, secalkyl or cycloalkyl, R" is alkylene, and R is alkyl or hydroxyalkyl are known (US. Pat. No. 3,478,096). They are shown to be useful in distillate fuels, including gasoline, as stabilizers (US. Pat. No. 3,637,358).

It has now been discovered that certain other ether amines are effective carburetor detergents.

SUMMARY OF THE INVENTION .Gasoline containing a carburetor detergent amount of ether amine selected from iii. mixtures containing (l) and (ii), wherein R is selected from C -C alkylgroups. C -C aryl groups, and (l C alkenyl groups, and L is C -C alkylene; additive concentrates suitable for blending into gasoline containing said ether amine detergent.

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention is gasoline containing a carburetor detergent amount of ether amine selected from iii. mixtures containing I and II.

Preferred gasoline compositions contain ether amine wherein L is CH -CI-I -CH More preferred gasoline compositions contain ether amine wherein L is CH CH CH and R is C4-C3 alkyl. More preferred gasoline compositions contain said ether amine mixture where L is CH CH CH and R is -C alkyl.

The group R in useful ether amines has from one to about 40 carbon atoms and includes aryl. alkenyl and alkyl groups. These groups may be substituted or unsubstituted; branched or linear; cyclic or acyclic.

The aryl R groups include alkaryl as well as aralkyl groups. Illustrative examples of suitable aryl R groups are phenyl. di-heptadecylphenyl, tolyl, tertbutylphenyl. 1,3.5-trimethylphenyl, naphthyl, biphenylyl, benzyl, 6-phenyl-n-hexyl and the like.

Illustrative examples of suitable C -C alkenyl R groups are propenyl, octadecenyl, tetracontenyl, oleyl, indenyl, linoleyl, decenyl, pentacosenyl and the like.

Examples of useful alkyl R groups are methyl, tetracontyl, isobutyl, 2-ethylhexyl, 2,4-demethylheptyl,

2,4,6-trimethylnonyl, undecyl, trieosyl, cyclohexyl, dotricontyl and the like.

Preferred R groups are C -C alkyl groups. Representative examples of these groups are n-butyl, neicosyl, decyl, isopentyl, sec-butyl, ethylcyclohexyl, cyclopentyl, dodecyl, pentadecyl, nonadecyl, octacosyl and the like.

More preferred alkyl R groups have 8 to 30 carbon atoms still more preferred alkyl R groups are C -C Illustrative of this last group are tetradecyl, eicosyl, 2- ethylhexyl, tetracosyl and the like.

The group L in the present ether amines is C -C alkylene. An alkylene group is a hydrocarbyl radical which has the general formula --C,,H Representative alkylene groups are and the like Illustrative examples of useful ether amines are 'CH -O-(CH -NI-I (C.,.,-H -OCH -};CH-

C H -O-(CH -NH 1,2-dimethyl-2- octadecyloxyethylamine, di(2-phenoxyethyl)amine, 4-tricosyloxy-n-butylamine, 6-(3-phenyl-n-propyloxy)- n-hexylamine, [C H OCH(CH )CH(CH- H-NH and the like and mixtures thereof. These mixtures include mixtures of only the primary ether amines, only the secondary ether amines or preferably mixtures containing both the primary and secondary amines.

More preferred ether amines of lFormulae I and II are those where L is CH -CH CH and R is as exemplified above. In other words, R substituted ethers of n-propyl amines are more preferred.

Most preferred ether amines are the Formulae I and II compound (and mixtures containing both) where L is (CH and R is hydrocarbon alkyl in C -C range, preferably C -C range, and more preferably C -C range.

Illustrative examples of most preferred amines are 3-methoxy-n-propylamine, 3-triacontyloxy-npropylamine, 3-cyclohexyloxy-n-propylamine, 3- tetracontyloxy-n-propylamine, 3-octyloxy-npropylamine, 3-tetracosyloxy-n-propylamine, 3,3-diethoxy-n-propylamine, 3,3-dieicosyloxy-n-propylamine, 3-tetrahydrofurfuryloxy-n-propylamine, 3,3-di-2- ethylhexyloxy-n-propylamine, 3 ,3-diisopropyloxy-npropylamine, 3-tert-butyloxy-n-propylamine and the like and mixtures thereof.

Methods for preparing the ether amines useful in the present invention are known. A most convenient method for preparing many of the ether amines and especially the more preferred ether amines is by hydrogenating the corresponding ether nitrile. The following equation illustrates this method of preparation CH CH Any suitable hydrogenation catalyst can be used. Metallic catalysts commonly used are nickel, rhodium and the like. Raney nickel is an especially useful catalyst.

ln addition to the primary amine which is the main product formed in this hydrogenation, the secondary amine [C H -O-(CH2)4CH NH and some tertiary amine [C H O--(Cl-1 CH N are also formed as products. The formation of the secondary and tertiary amines can be controlled or suppressed by using appropriate hydrogenation conditions, for example, by carrying out the hydrogenation process in the presence of ammonia. [See page 254, Chemistry of Urganic Compounds, Carl R. Noller, 3rd Ed. (1965)].

A convenient method of preparing the more preferred ether nitriles for hydrogenation is by cyanoethylating suitable organic hydroxy compounds. A general discussion of this cyanoethylation reaction is found in The Chemistry of Acrylonitrile," American Cyanamid Company (1951), and is incorporated herein by reference.

The cyanoethylation reaction is represented by the following equation:

Thus by choosing appropriate organic hydroxy compounds and preferably C1-C4" monohydroxy primary alkanols, cyanoethylating them, then hydrogenating the resultant nitrile, the more preferred ethers of propyl amine can be prepared.

Besides using individual C -C alkanols such as methanol, n-dodecanol and the like, mixtures of the alkanols can also be used. These alkanol mixtures may simply be blends ofindividual alcohols; for example, 50 C H --OH/ 50 C H --OH; 2 C H -OH/ 70 C H ,OH/ 20 C, H --OH/ 8 C H OH; 60 2-ethy1 n-hexanol/ 40 n-nonanol/ 33 C]H21-OH/ C12H25'OH and the O1 mlX- tures of useful alkanols can be cuts of or the entire product obtained from commercial processes such as the hydrolysis of aluminum trialkoxides produced by ethylene chain growth on trialkyl aluminum (chain growth alkanols). Particularly useful chain growth" alkanols are those obtained from the process described in U.S. Pat. Nos. 3,415,861 and 3,384,651.

A particularly useful mixture of such chain growth alkanols has the following general composition. The mixture contains primary monohydroxy alkanols of both the linear and branch types. These mixtures are referred to as C mixed alkanols.

TABLE 1 Mixed Alkanols The following is aspecific composition of a C1042 type mixture. The weight ratio of linearzbranched alkanols in the mixture is about 80:20.

TABLE 11 Number of Carbons Weight C C 3.16 m 71.93 C 24.29 u 0.60 C and higher 0.02

Another class of preferred chain growth alkanol mixtures have the following general composition. Again, they are primary monohydroxy alcohols, both branched and linear with branchedzlinear weight ratios of 25:75 to :25, preferably 40:60 to 60:40. These mixtures are referred to as C alkanols or alkanol mixtures.

TABLE 111 C Alkanols Number of Carbons Weight /t C 0 about 2 C about 18 about 45 C about 15 about 30 C about 10 about 20 C about 10 about 16 C about 9 about 14 C 0 about 12 32 0 about 9 C, 0 about 5 C 0 about 2 C 0 about 2 C 0 about l Specific C alkanol mixtures are presented in the following table.

TABLE IV C2". Alkanol Mixtures The following examples illustrate prepartion of useful ether amines.

EXAMPLE 1 To a mixture of n-butanol (18.5 g, 0.25 mole) and 0.5 g of tetrabutyl ammonium hydroxide (25 percent in methanol) in a ml flask was added acrylonitrile 14.3 g, 0.27 mole) so that the temperature did not exceed 35. The mixture was stirred for 1 hour at ambient temperature (nitrogen atmosphere), neutralized with 2 ml of glacial acetic acid and distilled to give 35 g (96 percent yield, 100 percent conversion) of colorless liquid, bp 1 12/35mm. Vapor phase chromatography (G.C.) analysis (12 feet X inch) indicated the presence of a major peak (99 percent pure) with a retention time of 12.6 min. The infrared (IR) spectrum had Example Ethe r Nit rile absorption at 2250 cm (-CN) and at 1.110 cm (C-OC) and the nuclear magnetic resonance (NMR) spectrum showed two overlapping triplets (4H) centered at 3.605 and 3.488 corresponding to the protons adjacent to oxygen; a triplet centered at 2.556 (2H) corresponding to the methylene group adjacent to the nitrile. This characterizes B-butoxy propio nitrile.

Active Raney-nickel catalyst was prepared and about 3.5 grams were charged to a 250 ml stainless steel autoclave containing 80 ml of absolute ethanol, 11.7 g (0.092 mole) B-butoxy propionitrile and 8 g (0.45 mole) of liquid ammonia. The autoclave was charged with hydrogen (600 psig) and heated to 85-95 with stirring. After 1.0 hr the autoclave was cooled, vented and flushed with nitrogen. The reaction mixture was filtered through Celite and distilled, bp 68-69/1 8 mm, to give 9.1 g of colorless liquid (75 percent yield, 100 percent conversion). Vapor phase chromatography analysis indicated one major peak (99 percent pure) having the same retention time as authentic 'y-butoxypropylamine [C,H -O'-(CH NH The pot residue from distillation was a solid material that was not characterized.

When primary alkanols, methanol, octanol, eicosanol, and E il -OH and C alkanols are used instead of n-butanol in the Example 1 process, the corresponding methoxy-, octyloxy-, eicosyloxy-, tetracontyloxyand C oxy-n-propylamines are obtained.

EXAMPLE 2 -CN] was added via a Hoke bomb by pressuring Ether Amine Hydrogenation Product 6 with ammonia at psig followed by hydrogen to 400 p The mixture was stirred at 100C. (pressure read 1.130 psig at C.. 1.200 psig at C) for 2.5 hours. After 0.5 hour. the pressure had dropped to about 300 psig and hydrogen was added to give 40Qpsig at C.

This mixed product was separatedbyfiactiona fdistillation into the primary and secondary amine components.

This example illustrates that a mixture of primary and secondary amines can also be obtained on hydrogenating an ether nitrile. These mixed products may be used as such in gasoline or they can be fractionated into the individual components if desired.

Mixtures of, e ther amines contain the primary/- secondary moieties in weight ratios ranging from 95/5 to 5/95, These mixtures may also contain from 0 to 5 percent by weight of the corresponding tertiary amine which in Example 2 would have l 4 9 z)3+3 A method of preparing ether amines is also described in German Pat. No. 1,094,748, issued Dec. 15, 1960.


Following is'a "tabulation of ether amines obtained by hydrogenating ether nitriles, using the hydrogenation procedure illustrated by Examples 1 and/or 2.

' s am-0% as-N E 1o 2' H2)4-CN 11 2o+H41+- -(CH CN A 8 NH2 12 cyelohexyloxgy butyronitrile 1 MHlE- HQE- N Example (cont) Ether Nitrile Ether Amine Hydrogenation Product gasoline in concentrations ranging from about to about 4000 parts per million by weight, preferably from 5-1 ,000 ppm, and more preferably from -400 ppm. Any gasoline suitable as a fuel for spark ignition internal combustion engines can be used. Gasoline is generally a blend of hydrocarbon having a boiling range of from about C. to about 225C, which occur naturally in petroleum; and suitable hydrocarbons made from petroleum by processes such as thermal and'catalytic cracking, reforming, hydrocracking, polymerization and the like. Hydrocarbon compositions of typical base gasolines are given below; percentages are by volume.

" TABLE v' EXAMPLE 25 to base gasoline A.

EXAMPLE 26 To base gasoline A was added 25 ppm of Base Gasoline of A B C D E F G H .l K

Aromatics 29.0 28.5 30.0 60 80 38 16 Olefinics 3.5 3.0 4.0 l0 20 20 7 l2 Saturatcs 67.5 68.5 66.0 50 90 100 20 72 EXAMPLE 21 To base gasoline A was added 50 ppm of hexyloxy-npropylamine.

EXAMPLE 22 A gasoline composition was prepared by adding 25 ppnl (if C|0 |2H21 25O'(CH2)3NH2 to base gasoline A.

EXAMPLE 23 To gasoline A was added 50 ppm of C H Each ot the Eiim'bie' 21-2 6 compositions also containcd 3.16 grams of lead per gallon as tetraethyllead. about 1.44 grams ofethylene dibromide per gallon and about 1.52 grams of ethylene dichloride per gallon. The

55 lead and halides were added as a commercial tetracthyllead fluid.

'4 EXAMPLE 27 A series of gasoline compositions is prepared by adding 5. 200, 500, and 1,000 ppm of C H,, O(CH -NH to each of base gasolines A through H.

EXAMPLE 28 A series of gasoline compositions is prepared by adding 50, 60, and ppm of CH O(CH ),;NH to each of base gasolines B, F, and .l.

EXAMPLE 29 4,000 ppm of is added to base gasoline H.

EXAMPLE 30 A series of compositions is prepared by blending 8, 10, 30, and 150 ppm of each of Examples 1-20 ether amines in base gasoline C.

EXAMPLE 31 A series of compositions is prepared by blending 5, 25, 75, 400, 1,500 and 2,000 ppm of each of the followingether amines in base gasoline B:

[C12H25O""(H2)H+2NH l 15 29 2)8+2 [CGHIB O(CHZ)3+2NH [CBH17 O '(CH2)3+2NH l l012 2125' 2)8+2 In addition to the ether amines, the gasoline compositions can also contain other additives such as tetramethyl lead, (methyl cyclopentadienyl) manganese tricarbonyl, or iron pentacarbonyl; blending agents such as diisopropyl ether and acetone; anti-icers such isopropanol, the carbitols; amines such as N-methyl aniline, aniline; deposit modifiers such as tris-(B- chloroisopropyl) thionophosphate, cresyldiphenyl phosphate, trimethyl phosphate, tricresylphosphate; metal deactivators such as N,N'-disalicylidenel,2- diamino propane; antioxidants such as substituted phenylene diamines, 2,6-di-tert-butyl phenyl, 2,6-ditert-butyl-a-dimethylamino-p-crsol; rust inhibitors, demulsifiers, dyes and the like.

Another embodiment ofthe present invention are additive concentrates of useful ether amines. These concentrates are blends of the ether amines in liquid carriers. The liquid carriers must be miscible with gasoline and are preferably aromatic or aliphatic hydrocarbons and mixtures thereof. Typical liquid carriers are hexane, toluene, isooctane, xylene, benzene, heptane and the like. The ether amine additive concentrates can oline.

Following are examples illustrating additive concentrates.

EXAMPLE 32 Concentrates are prepared containing 10 percent of each of the Example l-2O ether amine in toluene.

v EXAMPLE 33 A 90 percent Example 5 amine/ 10 percent hexane concentrate is prepared.

EXAMPLE 34 A 50/50 (by weight) blend of C H O(CH NH /decane is prepared.

EXAMPLE 3 5 A /30 (by weight) blend of Example 6 ether amine/isopropylbenzene is prepared.

EXAMPLE 36 A 40/60 (by weight) blend of Example 8 ether amine in benzene is prepared.

EXAMPLE 37 A concentrate containing 50 percent by weight of C H O-(CH NH in 50/50 (by weight) mixture of xylene/decane is prepared.

EXAMPLE 318 A concentrate containing percent by weight ot'the Example 18 amine in mixed nonanes is prepared.

Theether amine additives of the present invention are effective carburetor detergents in gasoline. The following Carburetor Detergency Test was used to illus- Following are the detergency results obtained for gasoline compositions of the present invention.

TABLE VI Carburetor Detergency Average of two runs. 2 M is a commercial carburetor detergent.

The data clearly shows that the present ether amines are effective carburetor detergents.

The present ether amines can also be advantageously combined with intake valve deposit reducing additives. e.g., such as those described in U.S. Pat. 3,502,45l. Especially useful intake valve deposit reducing additives are the 350-],500 molecular weight liquid polymers of mixtures of C and higher olefins described in copending application Ser. No. 66,]22, filed Aug. 21, 1970. The description therein is incorporated by reference.

These polymers are used in gasoline in concentrations ranging from about 4002,000 ppm, and preferably below about 1,000 ppm. These use concentrations can be combined with the ether amine in the gasoline use concentration described herein. The combination of these additives then provides gasoline with enhanced intake system detergency.


y 12 claims to invention follow.

I claim:

1. Gasoline containing a carburetor detergent amount of an ether amine having the formula R-O- LNH wherein R is C C alkyl and L is C -C alkylene.

2. The gasoline of claim 1 wherein R is C -C alkyl.

3. The gasoline of claim 1 wherein L is CH CH- 2 H2- 4. The gasoline of claim 3 wherein R is C -C alkyl.

5. .The gasoline of claim 4 wherein R is C C 6. The gasoline of claim 1 wherein R is a mixture of decyl and dodecyl.

7. The gasoline of claim 1 wherein R is derived from a mixture of C alkanols.

33 33 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 5 9, 5 Dated: November 19, 1974 Inventor (K) Michael Dubeck It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below;

rIn Column lines 9-3 0 that part of the formula reading n 2")CH should read -c ln Example 2#, Column 8, lines 26-28 that part of the two formulae reading H i should read H In Column 9, line 42 'phenyl" 'should be phenol Signed and sealed this 4th day of March 1975.

(SEAL) Attest:

C MARSHALL DANN RUTH C. I'iASON Commissioner of Patents attesting Officer and Trademarks I

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3478096 *Apr 18, 1966Nov 11, 1969Universal Oil Prod CoSec.-alkyl- or cycloalkyl-alkoxy-alkylamines
US3637358 *Mar 5, 1969Jan 25, 1972Universal Oil Prod CoStabilization of hydrocarbon oils
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3960965 *Oct 23, 1973Jun 1, 1976The British Petroleum Company LimitedGasoline composition
US3980450 *Aug 5, 1974Sep 14, 1976The British Petroleum Company LimitedGasoline composition
US4526587 *May 31, 1983Jul 2, 1985Chevron Research CompanyDeposit control additives-methylol polyether amino ethanes
US4537693 *May 31, 1983Aug 27, 1985Chevron Research CompanyLubricating oil compositions containing methylol polyether amino ethanes
US4604103 *Dec 16, 1985Aug 5, 1986Chevron Research CompanyDeposit control additives--polyether polyamine ethanes
US4684373 *Jul 31, 1986Aug 4, 1987Wynn Oil CompanyGasoline additive composition
US4964879 *Mar 27, 1989Oct 23, 1990Texaco Inc.Middle distillate fuel containing deposit inhibitor
US5024678 *Apr 5, 1988Jun 18, 1991Dea Mineralol AktiengesellschaftProcess for the prevention or reduction of deposits in carburetors, injection devices and similar devices of engines
US5511517 *Feb 10, 1994Apr 30, 1996Ethyl CorporationReducing exhaust emissions from otto-cycle engines
US6660050May 23, 2002Dec 9, 2003Chevron U.S.A. Inc.Method for controlling deposits in the fuel reformer of a fuel cell system
US8465560Jun 18, 2013Butamax Advanced Biofuels LlcGasoline deposit control additive composition
US8632638Nov 15, 2011Jan 21, 2014Chevron Oronite Company LlcMethod for cleaning deposits from an engine fuel delivery system
US9006126 *Jun 26, 2012Apr 14, 2015Shell Oil CompanyAdditive impregnated composition useful in the catalytic hydroprocessing of hydrocarbons, a method of making such catalyst, and a process of using such catalyst
US20130005566 *Jun 26, 2012Jan 3, 2013Shell Oil CompanyAdditive impregnated composition useful in the catalytic hydroprocessing of hydrocarbons, a method of making such catalyst, and a process of using such catalyst
EP0255115A1 *Jul 28, 1987Feb 3, 1988Wynn Oil CompanyGasoline additive composition
EP1431374A1Sep 16, 2003Jun 23, 2004Chevron Oronite Company LLCA method of reducing particulate emissions in internal combustion engines
WO1984004754A1 *May 29, 1984Dec 6, 1984Chevron ResMethylol polyether amino ethanes in fuel and lubricant compositions
WO1990010051A1 *Feb 20, 1990Sep 7, 1990Union Oil Company Of CaliforniaFuel composition for control of intake valve deposits
WO1997043360A1 *May 12, 1997Nov 20, 1997Chevron Chemical CompanyPolyalkylphenoxyaminoalkanes and fuel compositions containing the same
WO2010091069A1Feb 3, 2010Aug 12, 2010Butamax™ Advanced Biofuels LLCGasoline deposit control additive compositions
U.S. Classification44/434, 44/424
International ClassificationC10L1/22, C10L1/222
Cooperative ClassificationC10L1/22, C10L1/2225
European ClassificationC10L1/222B2, C10L1/22