US3701640A - Composition - Google Patents
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- US3701640A US3701640A US196241A US3701640DA US3701640A US 3701640 A US3701640 A US 3701640A US 196241 A US196241 A US 196241A US 3701640D A US3701640D A US 3701640DA US 3701640 A US3701640 A US 3701640A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
Definitions
- a preferred reaction product contains 4,7,l0-tris(2-hydroxy-S-alkyl) benzyltetraethylenepentamine-l,1 3 palmitic acid diamide.
- the present invention is directed to novel hydrocarbon gasoline compositions having improved detergency. More specifically, the present invention concerns the use as gasoline additives of reaction products of a monocarbox ylic acid or derivatives thereof, an alkyl-substituted phenol, a polyamine having at least three nitrogen atoms, at least two primary and at least one secondary, and formaldehyde and the modified derivatives thereof wherein the phenolic hydrogen is replaced by other groups.
- reaction products of a monocarboxylic acid or a derivative thereof, an alkyl-substituted phenol, a polyamine having at least three nitrogen atom, at least two primary and at least one secondary, and formaldehyde, and the modified derivatives thereof wherein the phenolic hydrogen is replaced by other groups provide compositions having excellent detergency when added to hydrocarbon gasolines in small amounts.
- An advantageous modification of the phenolic hydroxyl group of these reaction products is accomplished by the partial or complete neutralization thereof with basic materials, for instance ammonium and metal components such as their hydroxides, carbonates and bicarbonates.
- Metals of Groups IB, II-A, H-B, IV-A, V-A and VIII e.g. calcium, nickel, zinc, barium, iron, copper, cobalt, tin, lead and bismuth, are particularly useful.
- Specific, exemplary compounds which can be used to accomplish the neutralization of the phenolic hydroxyl group are ammonium hydroxide, calcium hydroxide, nickel hydroxide, zinc carbonate, iron carbonate, copper carbonate and cobalt bicarbonate.
- Another modification of the phenolic hydroxyl group is accomplished by the esterification or etherifica tion thereof.
- the phenolic hydroxyl group may be esterified or etherified either prior or subsequent, preferably prior, to the formation of the reaction products described herein.
- Suitable acids and alcohols useful in this modification often contain up to about -8 carbon atoms, e.g. acetic, propionic or butyri-c acids and methanol or ethnol.
- the esterification and etherification are accomplished by methods well known in the art.
- the sequence in which the reactants can be combined to afford the gasoline detergent additives of the present invention may be varied depending upon the products which are being prepared. Regardless of the sequence of reaction and reaction conditions, however, about 0.05 to 2 moles, preferably about 0.2 to 1 mole, of reactive carboxylic acid group (including an anhydride group as two such carboxyl groups) is generally reacted per average basic, reactive primary nitrogen atom present in one mole of the amine; and at least about 0.2 mole, preferably up to about 2 moles, of each of the alkylated phenol and formaldehyde per average basic reactive, secondary nitrogen atom present in a mole of amine reactant, is reacted.
- each of the alkylated phenol and formaldehyde is reacted in an amount of about 0.2 to 1 mole per average basic reactive, secondary nitrogen atom per mole of the amine.
- the carboxylic acid useful in the present invention is a monocarboxylic acid of from 2 to about 24 carbon atoms including the corresponding acid anhydrides, esters or acid halides, e.g. acid chlorides, of the carboxylic acids.
- the acid can be straight chain or branched, saturated or unsaturated, aliphatic (including cycloaliphatic), aromatic or heterocyclic.
- the preferred carboxylic acids are the ali phatic monocarboxylic acids of 4 to about 24 carbon atoms.
- Particularly suitable monocarboxylic acids and anhydrides are the saturated and unsaturated fatty acids, preferably of about 10 to 24 carbon atoms, such as lauric acid, stearic acid, palmitic acid, oleic acid, arachidic acid, myristic acid, linoleic acid and the like acids or mixtures thereof.
- the amine component of the reaction products of the invention is a polyamine having at least three nitrogen atoms, at least two primary and at least one secondary.
- Suitable polyamines of the invention include polyalkylene polyamines represented by the formula:
- n is a number of at least 2, commonly 2 to 10;
- R is an alkylene radical of 2 to about 25 carbon atoms,
- Non-limiting examples of the polyalkylenepolyamine reactants are diethylenetriamine; triethylenetetramine; tetraethylenepentamine; etc.
- the formaldehyde component may be present in any avaiable form of formaldehyde such as formalin, paraformaldehyde and such.
- THE ALKYLAT'E'D PH ENOL sulting product with the fourth component is generally carried out at a temperature of about 200 to 230 C., with the optimum reaction temperature being dependent primarily on the particular acid component selected. Again, the reactions proceed readily at atmospheric pressure, although suband superatmospheres of pressure can be utilized.
- the alkylated phenols may also contain one or more non-deleterious substituent groups.
- the present invention also contemplates use as the phenol component, aromatic derivatives other than phenyl derivatives as, for instance, alkylnaphthols and similar derivatives of biphenyl, terphenyl, phenanthrene, anthracene, etc.
- the sequence of reaction can vary.
- the monocarboxylic acid reactant may first be reacted with the polyamine component and the resulting product then reacted directly with the phenol component and the formaldehyde component.
- Reaction of the acid and amine may be conducted at a reaction temperature of about 1125 to 350 C., preferably about 190 to 280 C.
- Reaction of the resulting product with the phenol and the formaldehyde is usually conducted at a temperature of about 125 to 350 C., preferably about 190 to 280 C.
- Both of the reactions are conveniently carried out at atmospheric pressure but subor super-atmospheric pressures can be employed, if desired.
- the reaction may be carried out in bulk or in the presence of a mutual solvent for the reactants.
- the polyamine, phenol and formaldehyde can be reacted first and the condensation product of the three then reacted with the acid component which is preferably a fatty acid.
- Reaction of the polyamine, phenol and formaldehyde components can be carried out conveniently by heating the three-component mixture at a temperature of about 70 to 150 C. until essentially all water of reaction is removed. Reaction of the re- 3CH2O OH CH, N CHZCH
- the above scheme indicates that, for instance, if only one mole of formaldehyde and reactive phenol were used that only one benzyl alcohol grouping would be substituted on the reactive amino groups.
- the condensation products used in the gasoline compositions of this invention are characterized as having at least one reactive phenolic hydroxy group which remains unsubstituted or is modified with various groups as previously indicated.
- the gasoline-soluble metal salts, particularly the calcium salts are particularly eflective for the purposes of this invention.
- the salts can be prepared by neutralization of the condensation product with a basic compound of the metal as, for instance, the hydroxides, oxides, carbonates and the like or by neutralization with ammonium hydroxide followed by preparation of the metal salt by methathesis. Greater than stoichiometric equivalents of the metals can be used, if desired. to give basic salts.
- gasoline to which the additives of the present invention are incorporated is meant hydrocarbon fractions boiling primarily in the gasoline range, usually in the range of about to 425 F., often having added thereto a small amount, generally between about 1 to 6 cc. per gallon, preferably about 2 to 4 cc. per gallon, of a tetra-lower-alkyl lead compound as an anti-knock agent.
- the gasolines are usually composed of a major amount of a blend of hydrocarbon mineral oil fractions boiling primarily in the aforementioned range and will contain varying proportions of parafiins, olefins, napthenes and aromatics derived by distillation, cracking and other refining and chemical conversion processes practiced upon crude oil fractions.
- Straight run gasolines gasolines derived from cracking gas oil, gasolines or reformate from reforming straight run naphtha over a platinum-alumina catalyst in the presence of hydrogen, etc., are components frequently used in making up a gasoline composition.
- a typical premium gasoline besides containing a small amount of a tetra-lower-alkyl lead compound as an antiknock agent may also contain small amounts of other nonhydrocarbon constitutents used to impart various properties to the gasoline in its use in internal combustion engines, e.g., halohydrocarbon scavengers, oxidation, inhibitors, etc.
- Such gasolines frequently have a Research Method octane number of about 90 and 105, and a Motor Method octane number of about 80 to 98.
- reaction products described herein are incorporated in the gasoline in minor amounts sutficient to provide a composition exhibiting improved detergent properties.
- the actual amount of the additive employed may vary depending upon the particular gasoline employed, its lead content, etc. Often about 10 to 500 or more pounds of the detergent, preferably about 15 to 100 or 400 pounds per 1,000 barrels of gasolinne, are employed.
- Palmitic acid (768 g.), tetraethylenepentamine (284 g.) and 99 g. of mineral lubricating oil having a viscosity of 1505 SUS at 100 F. are introduced into a -liter, fournecked, round-bottom flask fitted with a mechanical stirrer, water separator, reflux condenser, thermometer, and nitrogen gas inlet.
- the mixture is heated and stirred for about 4 hours under a nitrogen blanket at about 100 C.
- the mixture is then allowed to cool overnight.
- EXAMPLE III Zinc neutralized A Product A is heated with stirring to 80 C. and 50 g. of water is added. Zinc carbonate (124 g.) is then added portionwise over about one-and-one-half hours. The reaction mixture is stirred an additional 3 hours at 80 C., and then slowly heated to 150 C. After cooling overnight, 3 liters of benzene are added and the mixture filtered. The benzene is then flash distilled ofi, giving 3816 g. of product.
- EXAMPLE IV Calcium neutralized A Product A is heated with stirring to 80 C. and 50 g. of water is added. Calcium hydroxide (75 g.) is then added portionwise over about one-and-one-half hours. The reaction mixture is stirred an additional 5 hours at 80 C. and then slowly heated to 150 C. After cooling overnight, 3 liters of benzene are added and the mixture filtered. The benzene is then flash distilled off, giving about 3800 g. of product.
- EXAMPLE VI The additives of present invention were evaluated in a 96-hour cycling test using a 1966 Chevrolet V-8 engine. To aggravate engine dirtiness, a slipsteam of exhaust gases was routed to the intake air cleaner. This flow and the PCV flow were adjusted to the same level at the start of each test, but then not further adjusted during the test.
- EXAMPLE VII A visual rating system provides another method of evalulating effectiveness of detergents. This rating system, shown in Table II, .was carried out at the conclusion of the test, after the engine was disassembled. A rating of indicates a perfectly clean part or surface, and lower numbers indicate respective degrees of dirtiness.
- composition of claim 1 wherein said component C is an alkylated phenol having at least one alkyl group of about 4 to about 20 carbon atoms and at least one reactive ortho or para position.
- component A is a fatty acid of about 10 to 24 carbon atoms.
- component B is a polyalkylene polyamine of the formula:
- n is from 2 to about 10 and R is alkylene of 2 to about 8 carbon atoms.
- composition of claim 2 wherein about 0.2 to 1 mole of reactive carboxylic acid group is reacted per average, reactive primary nitrogen atom per mole of component B.
- composition of claim 2 wherein the phenolic hydroxyl group of the reaction product is modified to form ammonium or metal salts thereof.
- composition of claim 2 wherein about 10 to 500 pounds of reaction product are present per one thousand barrels of gasoline.
- EXAMPLE III 8. The composition of claim 2 wherein the phenolic
- comparative photographs were taken of engine parts following the use of fuel containing calcium neutralized Product A as compared to fuel without calcium neutralized Product A.
- the rocker-arm covers and pan were decidedly cleaner than in the test without calcium-modified Product A.
- a gasoline composition comprising a hydrocarbon gasoline and a minor amount, sutficient to improve the detergent properties of said gasoline, of an additive which is the reaction product of:
- (C) a component selected from the group consisting of an alkylated phenol having at least one alkyl group of about 4 to 20 carbon atoms and at least one reactive hydroxyl group of said reaction product is modifiedto form an alkyl ester or alkyl etherthereof, said alkyl ester and alkyl ether containing up to about 8 carbon atoms.
- component A is a fatty acid which contains from about 10 to 24 carbon atoms; component B has a formula as follows:
- composition of claim 2 wherein a major component of said reaction product has the following formula:
- composition of claim 9 wherein R contains from 2 to about 10 carbon atoms and component C is said para alkyl substituted phenol.
- composition of claim 10 wherein the gasoline detergent additive is a metal or ammonium salt of the phenolic hydroxyl group of the reaction product.
- composition of claim 10 wherein said phenolic hydroxyl group of said reaction product is modified to form an alkyl ester or alkyl ether thereof, said alkyl ester and alkyl ether containing up to about 8 carbon atoms.
- composition of claim 11 wherein the metal is calcium.
- composition of claim 11 wherein the metal is nickel.
- composition of claim 11 wherein the metal is 16.
- composition of claim 10 wherein the reaction product contains a major portion of a 4,7,10-tri(2-hydroxy-S-alkyl)benzyltetraethylenepentamine-1,13 palmitic acid diamide.
- composition of claim 10 wherein about 10 to 500 pounds of reaction product are present per one thousand barrels of gasoline.
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Abstract
A HYDROCARBON GASOLINE COMPOSITION CONTAINING, AS AN ADDITIVE, A MINOR AMOUNT, SUFFICIENT TO IMPROVE THE DETERGENCY OF SAID GASOLINE, OF THE REACTION PRODUCT OF: (A) A MONOCARBOXYLIC ACID OR DERIVATIVE THEREOF; (B) A POLYAMINE HAVING AT LEAST THREE NITROGEN ATOMS, AT LEAST TWO PRIMARY AND AT LEAST ONE SECONDARY; (C) AN ALKYL-SUBSTITUTED PHENOL; AND (D) FORMALDEHYDE; A PREFERRED REACTION PRODUCT CONTAINS 4,7,10-TRIS(2-HYDROXY-5-ALKYL) BENZYLTERTRAETHYLENEPENTAMINE-1,13 PALMITIC ACID DIAMIDE.
Description
United States Patent 3,701,640 COMPOSITION Charles A. Lease, Chicago, Seymour H. Patinkin, Skokie, and Frank J. Chloupek, South Holland, 11]., assignors to Atlantic Richfield Company, New York, N.Y.
No Drawing. Continuation of application Ser. No.
44,612, June 8, 1970, now abandoned. This application Nov. 5, 1971, Ser. No. 196,241
Int. Cl. C101 N22 US. CI. 44-66 20 Claims ABSTRACT OF THE DISCLOSURE A hydrocarbon gasoline composition containing, as an additive, a minor amount, sufiicient to improve the detergency of said gasoline, of the reaction product of:
(A) a monocarboxylic acid or derivative thereof;
(B) a polyamine having at least three nitrogen atoms,
at least two primary and at least one secondary;
(C) an alkyl-substituted phenol; and
(D) formaldehyde;
A preferred reaction product contains 4,7,l0-tris(2-hydroxy-S-alkyl) benzyltetraethylenepentamine-l,1 3 palmitic acid diamide.
This application is a continuation of Ser. No. 44,612, filed June 8, 1970, now abandoned.
The present invention is directed to novel hydrocarbon gasoline compositions having improved detergency. More specifically, the present invention concerns the use as gasoline additives of reaction products of a monocarbox ylic acid or derivatives thereof, an alkyl-substituted phenol, a polyamine having at least three nitrogen atoms, at least two primary and at least one secondary, and formaldehyde and the modified derivatives thereof wherein the phenolic hydrogen is replaced by other groups.
Recently, increased engine deposits due largely to various emission control devices required on automobiles have been encountered in several critical engine areas. For instance, deposit build-ups occur in the PCV device and carburetor. These deposits upset normal PCV flow, idling speed and the air-fuel ratio; additionally, these deposits, aggravate further engine deposits such as sludge and varnish in the crankcase, piston, and rocker arm areas. This invention, however, provides gasoline detergent additives which reduce engine deposits even while operating with modern emission control devices.
In accordance with the present invention, it has been found that the reaction products of a monocarboxylic acid or a derivative thereof, an alkyl-substituted phenol, a polyamine having at least three nitrogen atom, at least two primary and at least one secondary, and formaldehyde, and the modified derivatives thereof wherein the phenolic hydrogen is replaced by other groups, provide compositions having excellent detergency when added to hydrocarbon gasolines in small amounts. An advantageous modification of the phenolic hydroxyl group of these reaction products is accomplished by the partial or complete neutralization thereof with basic materials, for instance ammonium and metal components such as their hydroxides, carbonates and bicarbonates. Metals of Groups IB, II-A, H-B, IV-A, V-A and VIII, e.g. calcium, nickel, zinc, barium, iron, copper, cobalt, tin, lead and bismuth, are particularly useful. Specific, exemplary compounds which can be used to accomplish the neutralization of the phenolic hydroxyl group are ammonium hydroxide, calcium hydroxide, nickel hydroxide, zinc carbonate, iron carbonate, copper carbonate and cobalt bicarbonate. Another modification of the phenolic hydroxyl group is accomplished by the esterification or etherifica tion thereof. The phenolic hydroxyl group may be esterified or etherified either prior or subsequent, preferably prior, to the formation of the reaction products described herein. Suitable acids and alcohols useful in this modification often contain up to about -8 carbon atoms, e.g. acetic, propionic or butyri-c acids and methanol or ethnol. The esterification and etherification are accomplished by methods well known in the art.
The sequence in which the reactants can be combined to afford the gasoline detergent additives of the present invention may be varied depending upon the products which are being prepared. Regardless of the sequence of reaction and reaction conditions, however, about 0.05 to 2 moles, preferably about 0.2 to 1 mole, of reactive carboxylic acid group (including an anhydride group as two such carboxyl groups) is generally reacted per average basic, reactive primary nitrogen atom present in one mole of the amine; and at least about 0.2 mole, preferably up to about 2 moles, of each of the alkylated phenol and formaldehyde per average basic reactive, secondary nitrogen atom present in a mole of amine reactant, is reacted. Advantageously, each of the alkylated phenol and formaldehyde is reacted in an amount of about 0.2 to 1 mole per average basic reactive, secondary nitrogen atom per mole of the amine.
The four reactants which are employed to form the reaction products of the invention will be described under separate headings.
THE MONOCARBOXYLIC ACID REACTANT The carboxylic acid useful in the present invention is a monocarboxylic acid of from 2 to about 24 carbon atoms including the corresponding acid anhydrides, esters or acid halides, e.g. acid chlorides, of the carboxylic acids. The acid can be straight chain or branched, saturated or unsaturated, aliphatic (including cycloaliphatic), aromatic or heterocyclic. The preferred carboxylic acids are the ali phatic monocarboxylic acids of 4 to about 24 carbon atoms. Particularly suitable monocarboxylic acids and anhydrides are the saturated and unsaturated fatty acids, preferably of about 10 to 24 carbon atoms, such as lauric acid, stearic acid, palmitic acid, oleic acid, arachidic acid, myristic acid, linoleic acid and the like acids or mixtures thereof.
POLYAM-INE REACTANT The amine component of the reaction products of the invention is a polyamine having at least three nitrogen atoms, at least two primary and at least one secondary. Suitable polyamines of the invention include polyalkylene polyamines represented by the formula:
wherein n is a number of at least 2, commonly 2 to 10; R is an alkylene radical of 2 to about 25 carbon atoms,
preferably 2 to about '8 carbon atoms. Non-limiting examples of the polyalkylenepolyamine reactants are diethylenetriamine; triethylenetetramine; tetraethylenepentamine; etc.
FORMALDEYHYDE REACTANT The formaldehyde component may be present in any avaiable form of formaldehyde such as formalin, paraformaldehyde and such.
THE ALKYLAT'E'D PH ENOL sulting product with the fourth component, e.g., the acid component, is generally carried out at a temperature of about 200 to 230 C., with the optimum reaction temperature being dependent primarily on the particular acid component selected. Again, the reactions proceed readily at atmospheric pressure, although suband superatmospheres of pressure can be utilized.
Numerous other ramifications of these methods can be used for preparing the additives of the invention. For example, in many instances, more than one monocarboxylic acid or anhydride reactant may be reacted with one or more of the polyamines of the invention. In addition, reaction products of the monocarboxylic acid component and the polyamine may be further reacted with phenolic condensation compounds of the polyamine, phenol and formaldehyde reactants in varying stoichiometric ratios within those described hereinabove.
The following is illustrative of the reactions that may be employed to produce the reaction products used in the gasoline compositions of the present invention.
(A) Monocarboxylic acid-l-polyalkylene polyamine with formaldehyde and alkyl phenol.
phenol, octyl phenol, nonyl phenol, p-tert-octyl phenol, l,l,3,3 tetramethylbutyl, phenol, a mixture of such phenols, and the like. If desired, the alkylated phenols may also contain one or more non-deleterious substituent groups. The present invention also contemplates use as the phenol component, aromatic derivatives other than phenyl derivatives as, for instance, alkylnaphthols and similar derivatives of biphenyl, terphenyl, phenanthrene, anthracene, etc.
As discussed above, the sequence of reaction can vary. For instance, the monocarboxylic acid reactant may first be reacted with the polyamine component and the resulting product then reacted directly with the phenol component and the formaldehyde component. Reaction of the acid and amine may be conducted at a reaction temperature of about 1125 to 350 C., preferably about 190 to 280 C. Reaction of the resulting product with the phenol and the formaldehyde is usually conducted at a temperature of about 125 to 350 C., preferably about 190 to 280 C. Both of the reactions are conveniently carried out at atmospheric pressure but subor super-atmospheric pressures can be employed, if desired. The reaction may be carried out in bulk or in the presence of a mutual solvent for the reactants.
Alternatively, the polyamine, phenol and formaldehyde can be reacted first and the condensation product of the three then reacted with the acid component which is preferably a fatty acid. Reaction of the polyamine, phenol and formaldehyde components can be carried out conveniently by heating the three-component mixture at a temperature of about 70 to 150 C. until essentially all water of reaction is removed. Reaction of the re- 3CH2O OH CH, N CHZCH The above scheme indicates that, for instance, if only one mole of formaldehyde and reactive phenol were used that only one benzyl alcohol grouping would be substituted on the reactive amino groups. Additionally, if an excess of mono carboxylic acid were used both primary reactive amino groups of the polyalkylene amine could form amide groups therewith. Thus, the final condensation products are normally mixtures of various reaction products dependent to a substantial extent upon the reaction conditions and mole ratios of various reactants.
The condensation products used in the gasoline compositions of this invention are characterized as having at least one reactive phenolic hydroxy group which remains unsubstituted or is modified with various groups as previously indicated. The gasoline-soluble metal salts, particularly the calcium salts, are particularly eflective for the purposes of this invention. The salts can be prepared by neutralization of the condensation product with a basic compound of the metal as, for instance, the hydroxides, oxides, carbonates and the like or by neutralization with ammonium hydroxide followed by preparation of the metal salt by methathesis. Greater than stoichiometric equivalents of the metals can be used, if desired. to give basic salts.
By the term gasoline to which the additives of the present invention are incorporated is meant hydrocarbon fractions boiling primarily in the gasoline range, usually in the range of about to 425 F., often having added thereto a small amount, generally between about 1 to 6 cc. per gallon, preferably about 2 to 4 cc. per gallon, of a tetra-lower-alkyl lead compound as an anti-knock agent. The gasolines are usually composed of a major amount of a blend of hydrocarbon mineral oil fractions boiling primarily in the aforementioned range and will contain varying proportions of parafiins, olefins, napthenes and aromatics derived by distillation, cracking and other refining and chemical conversion processes practiced upon crude oil fractions. Straight run gasolines, gasolines derived from cracking gas oil, gasolines or reformate from reforming straight run naphtha over a platinum-alumina catalyst in the presence of hydrogen, etc., are components frequently used in making up a gasoline composition. A typical premium gasoline, besides containing a small amount of a tetra-lower-alkyl lead compound as an antiknock agent may also contain small amounts of other nonhydrocarbon constitutents used to impart various properties to the gasoline in its use in internal combustion engines, e.g., halohydrocarbon scavengers, oxidation, inhibitors, etc. Such gasolines frequently have a Research Method octane number of about 90 and 105, and a Motor Method octane number of about 80 to 98.
The reaction products described herein are incorporated in the gasoline in minor amounts sutficient to provide a composition exhibiting improved detergent properties. The actual amount of the additive employed may vary depending upon the particular gasoline employed, its lead content, etc. Often about 10 to 500 or more pounds of the detergent, preferably about 15 to 100 or 400 pounds per 1,000 barrels of gasolinne, are employed.
The following examples further illustrate the present invention.
EXAMPLE I Preparation of the reaction product of palmitic acid, octylphenol, formaldehyde and tetraethylene pentamine Product A of the present invention can be prepared in the following manner:
Palmitic acid (768 g.), tetraethylenepentamine (284 g.) and 99 g. of mineral lubricating oil having a viscosity of 1505 SUS at 100 F. are introduced into a -liter, fournecked, round-bottom flask fitted with a mechanical stirrer, water separator, reflux condenser, thermometer, and nitrogen gas inlet. The mixture is heated and stirred for about 4 hours under a nitrogen blanket at about 100 C. The temperature is increased to about 150 C. over a twoand-one-half-hour period and 50 g. of water is collected (pH =11). The mixture is then allowed to cool overnight. Octylphenol (927 g.) and 750 g. of the same mineral oil are added to the reaction mixture and the mixture is heated to 90 C. Formaldehyde solution (38%, 366 g.) is added dropwise with stirring over about one-and-onehalf hours. Stirring is maintained throughout the addition and the temperature is held at 90-95 C. for an additional two-and-one-half hours. The temperature is then slowly increased to 150 C. and 292 g. of water are collected (pI-I =5), leaving the product designated A having a major component of the following formula:
about one-and-one-half hours. The mixture is stirred at 85 C. for 5 hours and then slowly heated to 150 C. Water g., pH=11) is collected, 240 g. of mineral lubricating oil having a viscosity of 150 SUS at F. added, and the mixture is then allowed to cool overnight. The mixture is diluted with 3 liters of benzene and filtered. The benzene is flash distilled off, giving 3828 g. of product.
EXAMPLE III Zinc neutralized A Product A is heated with stirring to 80 C. and 50 g. of water is added. Zinc carbonate (124 g.) is then added portionwise over about one-and-one-half hours. The reaction mixture is stirred an additional 3 hours at 80 C., and then slowly heated to 150 C. After cooling overnight, 3 liters of benzene are added and the mixture filtered. The benzene is then flash distilled ofi, giving 3816 g. of product.
EXAMPLE IV Calcium neutralized A Product A is heated with stirring to 80 C. and 50 g. of water is added. Calcium hydroxide (75 g.) is then added portionwise over about one-and-one-half hours. The reaction mixture is stirred an additional 5 hours at 80 C. and then slowly heated to 150 C. After cooling overnight, 3 liters of benzene are added and the mixture filtered. The benzene is then flash distilled off, giving about 3800 g. of product.
EXAMPLE V Nickel neutralized A" Product A is heated with stirring to 80 C. and 50 g. of water is added. Nickel hydroxide (66 g.) is then added portionwise over about one-and-one-half hours. The reaction mixture is stirred an additional 5 hours at 80 C. and then slowly heated to 150 C. After cooling overnight, 3 liters of benzene are added and the mixture filtered. The benzene is flash distilled 01f, giving 3800 g. of product.
In addition to the salts described above, other useful salts of the reaction product of Example I which can be prepared are those of copper and other metals.
EXAMPLE VI The additives of present invention were evaluated in a 96-hour cycling test using a 1966 Chevrolet V-8 engine. To aggravate engine dirtiness, a slipsteam of exhaust gases was routed to the intake air cleaner. This flow and the PCV flow were adjusted to the same level at the start of each test, but then not further adjusted during the test.
0 I ll CHKCHQHNHCH2CH2NCH2CH2NCHQCHaNCHzCHzNC (CH2)14CH3 I CH2 OR OR OR R R R wherein R is hydrogen and R is 1,1,3,3-tetramethylbutyl. Examples II through V describe product A modified with various neutralization agents.
EXAMPLE II Ammonium neutralized A Product A is heated with stirring to 80 C. and 125 g. of 28% ammonium hydroxide solution is added over The engine was completely overhauled (cleaned) between tests and a new PCV device installed. The PCV was 0 checked for deposit plugging at 24-hour intervals in a A commercial type laboratory leaded gasoline.
fuel plus 35 pounds of Calcium Neutralized Product A/ 1000 bbl. gasoline.
A commercial type laboratory leaded gasoline.
The differences in hour determinations reflect normal manufacturing tolerances in the new PCV devices used in the individual tests. Comparisons of data in the table show little change in flow (little deposit plugging) during the tests when the additive was used. For example, at 20 vacuum, 2.09 ftfi/min. flowed through the valve at the end of Test 3 compared to 2.11 at the start. In contrast, there were observed substantial changes in flow (indicating deposit plugging) on the tests without the additive. Again, at 20" vacuum, the flow dropped from 2.08 to 1.09 in Test 1 and from 2.00 to 1.41 in Test 4.
EXAMPLE VII A visual rating system provides another method of evalulating effectiveness of detergents. This rating system, shown in Table II, .was carried out at the conclusion of the test, after the engine was disassembled. A rating of indicates a perfectly clean part or surface, and lower numbers indicate respective degrees of dirtiness.
ortho or para position, an alkyl ester of said alkylated phenol, and alkyl ether of said alkylated phenol and mixtures thereof, said ester and ether linkages containing up to about 8 carbon atoms; and
(D) formaldehyde; wherein about 0.05 to 2 moles of reactive carboxylic acid group is reacted per average, reactive primary nitrogen atom per mole of component B, and components C and D are each reacted in an amount of about 0.2 to 2 moles per average basic, reactive secondary nitrogen atom per mole of component B.
2. The composition of claim 1 wherein said component C is an alkylated phenol having at least one alkyl group of about 4 to about 20 carbon atoms and at least one reactive ortho or para position.
3. The composition of claim 2 wherein component A is a fatty acid of about 10 to 24 carbon atoms.
4. The composition of claim 2 wherein component B is a polyalkylene polyamine of the formula:
wherein n is from 2 to about 10 and R is alkylene of 2 to about 8 carbon atoms.
5. The composition of claim 2 wherein about 0.2 to 1 mole of reactive carboxylic acid group is reacted per average, reactive primary nitrogen atom per mole of component B.
6. The composition of claim 2 wherein the phenolic hydroxyl group of the reaction product is modified to form ammonium or metal salts thereof.
7. The composition of claim 2 wherein about 10 to 500 pounds of reaction product are present per one thousand barrels of gasoline.
TABLE II Cleanliness ratings Rocker arm covers Right Left Pan Piiton s irt Detergent additive Varnish Sludge Varnish Sludge Varnish Sludge varnish None 10 9. 5 10 9. 5 10 9. 7 9.9 +35# /M bbl. calcium neutrahzed Prod A 10 10 10 10 10 9.9 9.9 -do 10 10 10 10 10 10 9. 9 +None 10 9. 3 9. 8 9. 1 10 9. 7
Commercial-type laboratory leaded gasoline.
EXAMPLE III 8. The composition of claim 2 wherein the phenolic In addition to the rating tests of the previous examples, comparative photographs were taken of engine parts following the use of fuel containing calcium neutralized Product A as compared to fuel without calcium neutralized Product A. In the test, using the calcium modified Product A, the rocker-arm covers and pan were decidedly cleaner than in the test without calcium-modified Product A.
I claim:
1. A gasoline composition comprising a hydrocarbon gasoline and a minor amount, sutficient to improve the detergent properties of said gasoline, of an additive which is the reaction product of:
(A) monocarboxylic acid of 2 to about 24 carbon atoms;
(B) polyamine having at least three nitrogen atoms,
at least two primary and at least one secondary;
(C) a component selected from the group consisting of an alkylated phenol having at least one alkyl group of about 4 to 20 carbon atoms and at least one reactive hydroxyl group of said reaction product is modifiedto form an alkyl ester or alkyl etherthereof, said alkyl ester and alkyl ether containing up to about 8 carbon atoms.
9. The composition of claim 1 wherein component A is a fatty acid which contains from about 10 to 24 carbon atoms; component B has a formula as follows:
18. The composition of claim 2 wherein a major component of said reaction product has the following formula:
OH OH OH 10. The composition of claim 9 wherein R contains from 2 to about 10 carbon atoms and component C is said para alkyl substituted phenol.
11. The composition of claim 10 wherein the gasoline detergent additive is a metal or ammonium salt of the phenolic hydroxyl group of the reaction product.
12. The composition of claim 10 wherein said phenolic hydroxyl group of said reaction product is modified to form an alkyl ester or alkyl ether thereof, said alkyl ester and alkyl ether containing up to about 8 carbon atoms.
13. The composition of claim 11 wherein the metal is calcium.
14. The composition of claim 11 wherein the metal is nickel.
15. The composition of claim 11 wherein the metal is 16. The composition of claim 10 wherein the reaction product contains a major portion of a 4,7,10-tri(2-hydroxy-S-alkyl)benzyltetraethylenepentamine-1,13 palmitic acid diamide.
17. The composition of claim 10 wherein about 10 to 500 pounds of reaction product are present per one thousand barrels of gasoline.
References Cited UNITED STATES PATENTS 3,498,766 3/1970 Gee et al 44-68 3,280,097 10/1966 Cizek 260- 4045 3,279,901 10/ 1966 Robbins et a1 4466 DANIEL E. WYMAN, Primary Examiner Y. H. SMITH, Assistant Examiner U.S. Cl. X.R.
zg gy UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 40 Dated October 31, 1972 Inventor(s)CharleS A. Lease Seymour H. Patinkin and Frank J.
Chloupek It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
|' Column 9 lines 4 to 11, delete the following structure? CH (CH CNHCH CH NCH CH NCH CH NCH CH NHLL'(CH CH OH OH OH R' R' R' Column 10, lines to 11, insert the following structure:
CH (CH CNHCH CH NCH l4 2 CH NCH Column 9, line 30, after the number 10-, delete "tri" and insert in place thereof --tris--.
CH NCH CH Signed and sealed this 6th day of March 1973.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents l. .J
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US19624171A | 1971-11-05 | 1971-11-05 |
Publications (1)
Publication Number | Publication Date |
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US3701640A true US3701640A (en) | 1972-10-31 |
Family
ID=22724580
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US196241A Expired - Lifetime US3701640A (en) | 1971-11-05 | 1971-11-05 | Composition |
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US (1) | US3701640A (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3944397A (en) * | 1974-03-07 | 1976-03-16 | E. I. Du Pont De Nemours And Company | Motor fuel composition containing mannich condensation products |
US4108783A (en) * | 1974-04-09 | 1978-08-22 | The Lubrizol Corporation | Haloalkyl hydroxy-aromatic condensation products as fuel and lubricant additives |
EP0003479A1 (en) * | 1978-02-11 | 1979-08-22 | Schering Aktiengesellschaft | Hardening agents and process for preparing epoxy resin polyadducts |
US4179449A (en) * | 1974-04-09 | 1979-12-18 | The Lubrizol Corporation | Haloalkyl hydroxy-aromatic condensation products as fuel and lubricant additives |
US4194886A (en) * | 1974-04-09 | 1980-03-25 | The Lubrizol Corporation | Haloalkyl hydroxy-aromatic condensation products as fuel additives |
US4205960A (en) * | 1974-04-09 | 1980-06-03 | The Lubrizol Corporation | Hydroxyalkyl hydroxy-aromatic condensation products as fuel and lubricant additives |
US4234414A (en) * | 1978-09-28 | 1980-11-18 | The Dow Chemical Company | Phosphate beneficiation process |
US4285824A (en) * | 1979-01-22 | 1981-08-25 | The Lubrizol Corporation | Hydroxyalkyl hydroxy-aromatic condensation products as fuel and lubricant additives |
US4343740A (en) * | 1980-02-22 | 1982-08-10 | The Lubrizol Corporation | Hydroxylalkyl hydroxy-aromatic condensation products as fuel and lubricant additives |
US5306313A (en) * | 1988-02-29 | 1994-04-26 | Exxon Chemical Patents Inc. | Dispersant additive comprising the reaction product of a polyanhydride and a mannich condensation product |
-
1971
- 1971-11-05 US US196241A patent/US3701640A/en not_active Expired - Lifetime
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3944397A (en) * | 1974-03-07 | 1976-03-16 | E. I. Du Pont De Nemours And Company | Motor fuel composition containing mannich condensation products |
US4108783A (en) * | 1974-04-09 | 1978-08-22 | The Lubrizol Corporation | Haloalkyl hydroxy-aromatic condensation products as fuel and lubricant additives |
US4179449A (en) * | 1974-04-09 | 1979-12-18 | The Lubrizol Corporation | Haloalkyl hydroxy-aromatic condensation products as fuel and lubricant additives |
US4194886A (en) * | 1974-04-09 | 1980-03-25 | The Lubrizol Corporation | Haloalkyl hydroxy-aromatic condensation products as fuel additives |
US4205960A (en) * | 1974-04-09 | 1980-06-03 | The Lubrizol Corporation | Hydroxyalkyl hydroxy-aromatic condensation products as fuel and lubricant additives |
EP0003479A1 (en) * | 1978-02-11 | 1979-08-22 | Schering Aktiengesellschaft | Hardening agents and process for preparing epoxy resin polyadducts |
US4234414A (en) * | 1978-09-28 | 1980-11-18 | The Dow Chemical Company | Phosphate beneficiation process |
US4285824A (en) * | 1979-01-22 | 1981-08-25 | The Lubrizol Corporation | Hydroxyalkyl hydroxy-aromatic condensation products as fuel and lubricant additives |
US4343740A (en) * | 1980-02-22 | 1982-08-10 | The Lubrizol Corporation | Hydroxylalkyl hydroxy-aromatic condensation products as fuel and lubricant additives |
US5306313A (en) * | 1988-02-29 | 1994-04-26 | Exxon Chemical Patents Inc. | Dispersant additive comprising the reaction product of a polyanhydride and a mannich condensation product |
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