JP2001240880A - Fuel additive composition containing mannich condensate and hydrocarbon group-substituted polyoxyalkyleneamine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fuel additive composition effective for preventing and suppressing the plugging of an engine oil screen. SOLUTION: This new fuel additive composition comprises (a) a Mannich condensate obtained by reacting (1) a high-molecular-weight alkyl-substituted hydroxy aromatic compound, (2) an amine and (3) an aldehyde in a molar ratio of the components (1):(2):(3) regulated so as to be 1:(0.1-10):(0.1-10), and (b) a hydrocarbon group-substituted polyoxyalkyleneamine or a fuel-soluble salt thereof, regulated so that the weight ratio of the polyoxyalkyleneamine to the Mannich condensate may be about 0.5:1 to about 12:1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fuel additive composition containing a Mannich condensate and a hydrocarbon-substituted polyoxyalkyleneamine. The invention further relates to the use of these additive compositions in fuel compositions to prevent and control clogging of engine oil screens.

[0002]

2. Description of the Related Art In the engine of an automobile, deposits are formed on the components of the engine, for example, the surface of a carburetor port, a throttle body, a fuel injector, an intake port, an intake valve, and a combustion chamber by oxidation and polymerization of a hydrocarbon fuel. It is well known that this is the case. These deposits, even when present in relatively small amounts, often cause significant operational performance problems such as stalls and insufficient acceleration. In addition, engine deposits significantly increase vehicle fuel consumption and the generation of exhaust pollutants. Therefore, it is very important to develop effective fuel detergents or deposit control additives to prevent or control such deposits, and a large number of such materials are of interest. Known in the field.

For example, polyoxyalkyleneamines, or polyetheramines, have been found to reduce engine deposits when used in fuel compositions. 1992
U.S. Pat. No. 5,112,364 (Las, et al.) Issued May 12, 1980 describes polyetheramines and / or polyetheramine derivatives with 10 to 200 parts per million.
A gasoline engine fuel oil containing 0 parts by weight is disclosed,
The polyetheramine is produced by reductive amination of a phenol- or alkylphenol-derived polyether alcohol with ammonia or a primary amine.

[0004] US Patent No. 5, issued August 26, 1997.
No. 660601 (Oppenlander et al.) Discloses gasoline engine fuels containing 10 to 2000 mg of alkyl-terminated polyetheramines per kg of fuel, the alkyl groups of which have 2 to 30 alkyl groups. It contains carbon atoms and the polyether moiety contains 12 to 28 butylene oxide units. The patent further teaches that polyetheramines are prepared by the reaction of an alcohol with butylene oxide, followed by amination with ammonia or an amine.

[0005] US Patent No. 43 issued June 1, 1982
No. 32595 (Herbstmann, et al.) Discloses a gasoline detergent comprising a hydrocarbon-substituted polyoxypropylenediamine, wherein the hydrocarbon substituent is from 8 to 1
Contains 8 carbon atoms. The patent further discloses that the additive comprises reductive amination of the hydrocarbon-substituted polyoxypropylene alcohol with ammonia to polyoxypropylene amine, which is then reacted with acrylonitrile,
It is taught to be prepared by making the corresponding N-2-cyanoethyl derivative. Next, hydrogenation in the presence of ammonia gives the desired hydrocarbon-substituted polyoxypropylene N-3-aminopropylamine.

[0006] US Patent No. 3 issued April 22, 1969
No. 440029 (Little et al.) Discloses a gasoline deicing agent which is a hydrocarbon-substituted polyoxyalkyleneamine, wherein the hydrocarbon substituent contains from 8 to 24 carbon atoms. The patent further states that the additives
It is taught that after condensation of the hydroxy compound with the alkylene oxide or alkylene oxide mixture, the terminal amino groups may be attached by reductive amination or cyanoethylation, followed by hydrogenation to produce by known methods. I have. Alternatively, the hydroxy compound or its oxyalkylated derivative may be reacted with bis (2-chloroethyl) ether and alkali to produce a chlorine-terminated compound, which is then reacted with ammonia to convert the amine to a terminal group. To produce a final product.

US Patent No. 4, issued January 27, 1981
No. 247301 (Honen) discloses hydrocarbon-substituted poly (oxyalkylene) polyamines,
The hydrocarbon group contains 1 to 30 carbon atoms, and the polyamine group contains 2 to 12 amine nitrogen atoms and 2 to 40 carbon atoms.
Contains carbon atoms. The patent further discloses that the additive comprises reacting a suitable hydrocarbon-terminated polyether alcohol with a halogenating agent such as HCl, thionyl chloride or epichlorohydrin to form a polyether chloride, It teaches that it may be prepared by reacting a polyether chloride with a polyamine to produce the desired poly (oxyalkylene) polyamine. The patent also teaches in Example 6 that the polyether chloride may be reacted with ammonia or dimethylamine to form the corresponding polyetheramine or polyetherdimethylamine.

[0008] US Patent No. 5, issued May 19, 1998
No. 7,529,991 (Plabak) discloses a fuel composition containing about 50 to about 2500 parts per million by weight of long chain alkylphenyl polyoxyalkyleneamines, wherein the alkyl substituent on the phenyl ring has at least 40
Has carbon atoms.

[0009] Mannich condensates are also known in the art as fuel additives for the prevention and control of engine deposits. For example, U.S. Pat. No. 4,231,759 issued Nov. 4, 1980 (Udelhofen, et al.)
Disclose high molecular weight alkyl-substituted hydroxyaromatic compounds, amines containing an amino group with at least one active hydrogen atom, and reaction products obtained by Mannich condensation of aldehydes such as formaldehyde. I have. The patent further teaches that such Mannich condensates are useful fuel detergents for carburetor surface and intake valve deposit control.

US Pat. No. 55, issued May 7, 1996
No. 14190 (Cunningham, et al.) Describes (a)
Intake air comprising a Mannich reaction product of a high molecular weight alkyl-substituted phenol, an amine and an aldehyde, (b) a poly (oxyalkylene) carbamate, and (c) a poly (oxyalkylene) alcohol, glycol or polyol, or a mono or diether thereof. A fuel additive composition for valve deposit control is disclosed.

The specification of US Pat. No. 5,697,988 issued December 16, 1997 (Malfa, et al.) Includes:
(A) a Mannich reaction product of a high molecular weight alkyl-substituted phenol, amine and aldehyde, (b) a polyoxyalkylene compound, preferably a polyoxyalkylene glycol or a monoether derivative thereof, and (c) optionally a poly-alpha-olefin. A fuel additive composition is disclosed that provides a reduction in fuel injectors, intake valves and combustion chamber deposits consisting of:

[0012]

Although it is generally known that hydrocarbon-substituted polyoxyalkyleneamines are effective deposit control fuel additives, especially in engine intake systems and combustion chambers. Certain polyoxyalkyleneamines have now been found to cause crankcase sludge and varnish buildup, which can eventually lead to clogging of engine oil screens (filtration screens) and catastrophic engine failure. . Accordingly, there is a need in the art for a polyoxyalkyleneamine-containing fuel additive composition that effectively inhibits intake system and combustion chamber deposits without causing the problem of engine oil screen clogging.

Accordingly, it is an object of the present invention to provide a fuel additive composition which prevents and suppresses clogging of an engine oil screen.

[0014]

SUMMARY OF THE INVENTION The combination of certain Mannich condensates with certain hydrocarbon-substituted polyoxyalkyleneamines provides an interesting fuel additive composition that provides excellent control of engine oil screen clogging. Giving is found this time.

Accordingly, it is an object of the present invention to provide a novel fuel additive composition comprising the following components: (a) (1) a high molecular weight alkyl group having a number average molecular weight of about 300 to about 5000; An alkyl-substituted hydroxyaromatic compound, (2) an amine containing an amino group having at least one active hydrogen atom, and (3) an aldehyde, and the molar ratio of each reactant (1), (2) and (3) Is from 1: 0.1 to 10: 0.1 to 10; and (b) a hydrocarbon-substituted polyoxyalkyleneamine represented by the following formula (I) or a fuel-soluble salt thereof:

[0016]

Embedded image

Wherein R is a hydrocarbon group having about 1 to about 30 carbon atoms; _one of R ₁ and R ₂ is methyl or ethyl and the other is hydrogen, R ₁
And R ₂ are each —O—CHR ₁ —CHR ₂
A is independently selected for each unit; A is amino, N-alkylamino having from about 1 to about 20 carbon atoms in the alkyl group,
Each alkyl group has from about 1 to about 20 N, N-dialkylamino or amine nitrogen atoms from about 2 to about 1 carbon atoms.
2 is a polyamine group having about 2 to about 40 carbon atoms;
And x is an integer of about 5 to about 100.] However, the weight ratio of the polyoxyalkyleneamine to the Mannich condensate is about 0.5: 1 to about 12: 1.

The present invention also provides a major amount of a hydrocarbon oil having a boiling point in the gasoline or diesel fuel boiling range;
It is another object of the present invention to provide a fuel composition comprising an effective amount of the fuel additive composition of the present invention for suppressing clogging of an engine oil screen.

[0019] The present invention further relates to a method comprising:
A fuel concentrate comprising an inert, stable, lipophilic organic solvent having a boiling point in the range of F (about 65 ° C. to about 205 ° C.) and about 10 to about 70% by weight of the fuel additive composition of the present invention. There is also to provide.

The present invention primarily relates to the interesting combination of certain Mannich condensates with certain hydrocarbon-substituted polyoxyalkyleneamines when clogging of engine oil screens occurs when used as an additive in fuel compositions. It is based on the surprising discovery that it provides excellent control of

[0021]

DETAILED DESCRIPTION OF THE INVENTION I) Mannich Condensate The Mannich reaction product used in the present invention has a number average molecular weight of an alkyl substituent of about 300 to about 5000 (Mn).
Wherein the alkyl-substituted hydroxyaromatic compound, preferably a polyalkyl substituent, has a number average molecular weight of about 300 to about 5;
Polyalkyl phenols derived from 1 000, more preferably from about 400 to about 3000 1-mono-olefin polymers; amines containing at least one> NH group, preferably alkylene polyamines of the formula:

[0022]

[Image Omitted] H ₂ N- (B-NH) _m -H

Wherein B is a divalent alkylene group having 1 to about 10 carbon atoms and m is an integer of 1 to about 10; and an aldehyde, preferably formaldehyde, is condensed in the presence of a solvent. It is obtained by doing.

The high molecular weight Mannich reaction product useful as an additive in the fuel additive composition of the present invention is preferably prepared by subjecting the above reactants to high molecular weight alkyl-substituted products according to conventional methods used in the preparation of Mannich condensates. It is prepared using hydroxyaromatic compounds, amines and aldehydes, with the respective molar ratios being approximately 1.0: 0.1 to 10: 1 to 10. Suitable condensation operations include room temperature to
At a temperature of about 95 ° C., an amine and an alkyl-substituted hydroxyaromatic compound, alone or in an easily removable organic solvent such as benzene, xylene or toluene, or in a solvent-purified neutral oil, at a temperature of about 95 ° C. In addition to the mixture with the group III compound, this involves heating the reaction mixture at an elevated temperature (120 ° C. to 175 ° C.) while distilling off the water of the reaction upwards. The reaction product thus obtained is worked up by filtration and, if desired, dilution with a solvent.

The Mannich reaction product additive used in the present invention preferably comprises an alkylphenol, ethylene polyamine and formaldehyde in a molar ratio of each reactant of from 1.0: 0.5 to 2.0: 1.0 to 1.0. As 3.0,
It is derived from a high molecular weight Mannich condensate formed by the reaction. Here, the number average molecular weight (Mn) of the alkyl group of the alkylphenol is from about 300 to about 500.
0. Representative high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol, polybutylphenol, and other polyalkylphenols, with polyisobutylphenol being most preferred. Polyalkylphenol is obtained by alkylating phenol with high molecular weight polypropylene, polybutylene and other polyalkylene compounds in the presence of an alkylation catalyst such as BF ₃ to form a number average molecular weight (Mn) on the benzene ring of the phenol.
Can be obtained by providing from about 300 to about 5000 alkyl substituents.

The alkyl substituent of the hydroxyaromatic compound can be derived from high molecular weight polypropylene, polybutene, and other polymers of mono-olefins, primarily 1-mono-olefins. Copolymers of mono-olefins with copolymerizable monomers, wherein the copolymer molecules contain at least 90% by weight of mono-olefin units can also be used. A particular example is a copolymer of butenes (butene-1, butene-2, and isobutylene) and a copolymerizable monomer, wherein the copolymer molecules comprise at least 90% by weight of propylene and butene units. There are things that include each. As the monomer copolymerizable with propylene or the butene, non-reactive polar groups that do not significantly reduce the oil solubility of the polymer, such as chloro,
Mention may be made of monomers containing a low proportion of bromo, keto, ether or aldehyde. The comonomer polymerized with propylene or the butene may be aliphatic or may contain non-aliphatic groups such as styrene, methylstyrene, p-dimethylstyrene, divinylbenzene, and the like. From the above restrictions imposed on propylene or the monomer copolymerizing with the butene, it is clear that the polymer and the copolymer of propylene and the butene are substantially aliphatic hydrocarbon polymers. Thus, the resulting alkylated phenol substantially contains an alkyl hydrocarbon substituent having a number average molecular weight (Mn) of about 300 to about 5000.

In addition to the above high molecular weight hydroxyaromatic compounds, other phenolic compounds which can be used include, among others, resorcinol, hydroquinone, cresol, catechol, xylenol, hydroxy-di-phenyl, benzylphenol, phenethylphenol , Naphthol and tolynaphthol. For the preparation of such preferred Mannich condensates, polyalkylphenol reactants, such as polypropylphenol and polybutylphenol, especially polyisobutylphenol, are preferred, the number average molecular weight of which alkyl group is from about 300 to about 5000, preferably about 400 ~ 300
0, more preferably about 500 to about 2000, and most preferably about 700 to about 1500.

As mentioned above, the polyalkyl substituents of the polyalkylhydroxyaromatic compounds used in the present invention are generally polymers or copolymers of mono-olefins, especially 1-mono-olefins such as ethylene, propylene and butylene. It can be derived from a polyolefin which is a polymer. The mono-olefin used preferably has 2 to about 24 carbon atoms, more preferably about 3 to 12 carbon atoms. More preferred mono-olefins include propylene, butylene, especially isobutylene, 1-octene and 1-decene. Polyolefins made from such mono-olefins include polypropylene, polybutene, especially polyisobutene, and polyalphaolefins made from 1-octene and 1-decene.

Preferred polyisobutenes used to prepare the polyalkylhydroxyaromatic compounds used in the present invention are those having at least about 20%, preferably at least about 50%, of the highly reactive methylvinylidene isomer.
And more preferably a polyisobutene containing at least about 70% of the methylvinylidene isomer. Suitable polyisobutenes include those prepared using BF ₃ catalysts. For the preparation of such polyisobutenes in which the methylvinylidene isomer accounts for a high proportion of the total composition, see US Pat.
No. 8 is described in each specification.

Examples of suitable polyisobutenes having a high alkylvinylidene content include Ultrabis 10, polyisobutene having a molecular weight of about 950 and a methylvinylidene content of about 76%, and Ultrabis 30, a molecular weight of about 1300.
And polyisobutene having a methylvinylidene content of about 74%, both of which are available from British Petrolium. Also, Glissopal (Gli
ssopal) 1000, 1300 and 2200 are B
Available from ASF.

The preferred configuration of the alkyl-substituted hydroxyaromatic compound is that of a para-substituted mono-alkylphenol. However, any alkylphenol that can be easily reacted by the Mannich condensation reaction may be used. Thus, ortho mono-alkyl phenols and dialkyl phenols are suitable for use in the present invention.

Representative amine reactants are alkylene polyamines, primarily polyethylene polyamines. Other representative organic compounds containing at least one HN <group suitable for use in the preparation of Mannich reaction products are also well known, and include mono- and di-aminoalkanes and their substituted analogs such as ethylamine Dimethylamine, dimethylaminopropylamine and diethanolamine; aromatic diamines such as phenylenediamine, diaminonaphthalene; heterocyclic amines such as morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine and piperidine; melamine and its substituted homologs. Can be.

[0033] The alkylene polyamine reactants useful in the present invention include linear, branched or cyclic polyamines, wherein each alkylene group contains from about 1 to about 10 carbon atoms; And / or mixtures of cyclic polyamines. Preferred polyamines are polyamines containing 2 to 10 nitrogen atoms per molecule or polyamine mixtures containing an average of about 2 to about 10 nitrogen atoms per molecule, such as ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine. Amines, pentaethylenehexamine, hexaethylenepeptamine, peptaethylenoctaamine, octaethylenenonaamine, nonaethylenedecaamine, and mixtures of such amines. Corresponding propylene polyamines, such as propylene diamine, dipropylene triamine, tripropylene tetraamine,
Tetrapropylene pentaamine and pentapropylene hexaamine are also suitable reactants. Particularly preferred polyamines are polyamines or mixtures of polyamines having about 3 to 7 nitrogen atoms, and most preferred are diethylene triamines or combinations or mixtures of ethylene polyamines whose physical and chemical properties are close to those of diethylene triamine. In selecting a suitable polyamine, consideration should be given to the compatibility of the resulting detergent and dispersant with the gasoline fuel mixture to be mixed.

In general, the most preferred polyamines, diethylenetriamines, are those having a physical and / or chemical composition that is generally close to the composition of diethylenetriamine, but with small amounts of branched or cyclic, and triethylenetetraamine or tetraethylenetriamine. It consists of a commercially available mixture that may also contain linear polyethylene polyamines such as ethylene pentaamine. For best results, such a mixture should contain at least 50% by weight, preferably at least 7% by weight of a linear polyethylene polyamine containing a large amount of diethylenetriamine.
It should contain 0% by weight.

The alkylene polyamine is usually obtained by reacting ammonia with a dihaloalkane such as dichloroalkane. Thus, alkylene polyamines are obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloroalkanes having 2 to 6 carbon atoms and chlorine on separate carbon atoms.

Representative aldehydes used in the preparation of the high molecular weight Mannich reaction product used in the present invention include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaaldehyde. Aldehydes and stearaldehyde can be mentioned. Aromatic aldehydes that may be used include benzaldehyde and salicylaldehyde. Exemplary heterocyclic aldehydes used in the present invention include furfural and thiopenaldehyde. A reagent that produces formaldehyde such as paraformaldehyde or a water-soluble formaldehyde solution such as formalin can also be used. Most preferred is formaldehyde or formalin.

II) Hydrocarbon-substituted polyoxyalkyleneamine The hydrocarbon-substituted polyoxyalkyleneamine used in the present invention has the following general formula (I).

[0038]

Embedded image

Wherein R, R ₁ , R ₂ , A and x are as defined above.

In the general formula (I), R represents about 1 carbon atom.
From about 30 hydrocarbon groups. Preferably, R is an alkyl or alkylphenyl group. More preferably, R is an alkylphenyl group wherein the alkyl portion is straight or branched chain alkyl having about 1 to about 24 carbon atoms.

In the general formula (I), R ₁ and R ₂
One is methyl or ethyl and the other is hydrogen. In other words, the oxyalkylene unit may be oxypropylene or oxybutylene.
Mixtures of oxypropylene and oxybutylene units are also contemplated for use in the present invention. Preferably, _one of R ₁ and R ₂ is methyl and the other is hydrogen. That is, a preferred oxyalkylene unit is oxypropylene.

Generally, A is amino; an N-alkylamino having from about 1 to about 20, preferably from about 1 to about 6, and more preferably from about 1 to about 4 carbon atoms in the alkyl group; Each alkyl group has about 1 to about 20 carbon atoms,
Preferably N, N-dialkylamino having about 1 to about 6, more preferably about 1 to about 4 carbon atoms; or about 2 to about 12 amine nitrogen atoms and about 2 to about 2 carbon atoms.
It is a polyamine moiety having about 40, preferably about 2 to 12 amine nitrogen atoms and about 2 to 24 carbon atoms. More preferably, A is a polyamine moiety derived from a polyalkylene polyamine including amino or alkylenediamine. Most preferably, A is amino or a polyamine moiety derived from ethylenediamine or diethylenetriamine.

X is preferably an integer from about 5 to about 50, more preferably from about 8 to about 30, and most preferably from about 10 to about 25.

The compounds used in the present invention generally have a molecular weight sufficient to be non-volatile at standard operating temperatures of the engine intake valves (about 200 ° C. to 250 ° C.). Normally,
The molecular weight of the polyoxyalkyleneamine compound used in the present invention ranges from about 600 to about 1000.

Fuel soluble salts of the compounds of general formula (I) can be readily synthesized for compounds containing amino or substituted amino groups, and such salts prevent or inhibit engine deposits. It seems to be useful. Suitable salts include, for example, those obtained by protonating the amino moiety with a strong organic acid such as an alkyl or aryl sulfonic acid. Preferred salts are derived from toluenesulfonic acid and methanesulfonic acid.

Definitions As used herein, the following terms have the following meanings, unless otherwise indicated. "Amino" means a group represented by -NH _2. “N-alkylamino” means a group represented by —NHR _a , where R _a is an alkyl group. “N, N-dialkylamino” means a group represented by —NR _b R _c , where R _b and R _c are alkyl groups.

"Hydrocarbon" means an organic radical mainly consisting of carbon and hydrogen, which may be aliphatic, cycloaliphatic, aromatic or a combination thereof, for example aralkyl or alkaryl. Such hydrocarbon groups are generally not aliphatically unsaturated, ie, olefinic or acetylenically unsaturated, but may contain minor amounts of heteroatoms, for example oxygen or nitrogen, or halogens such as chlorine.

"Alkyl" refers to both straight and branched chain alkyl groups. "Lower alkyl" means an alkyl group having 1 to about 6 carbon atoms, including primary, secondary and tertiary alkyl groups. Representative lower alkyl groups include, for example, methyl, ethyl, n-propyl,
Examples thereof include isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl and the like.

"Alkylene" refers to straight and branched chain alkylene groups having at least 2 carbon atoms. Representative alkylene groups include, for example, ethylene (-CH
₂ CH ₂ —), propylene (—CH ₂ CH ₂ CH ₂ —), isopropylene (—CH ₂ (CH ₃ ) CH ₂ —), n-butylene (—CH ₂ CH ₂ CH ₂ CH ₂ —), sec - butylene _{(-CH (CH 2 CH 3)} CH 2 -), n- pentene (-
_{CH 2 CH 2 CH 2 CH 2} CH 2 -) and the like "polyalkylene" refers to a polymer or oligomer having the general formula.

[0050]

Embedded image

[Wherein R _i and R _j are each independently:
Hydrogen or a lower alkyl group, and y is an integer from about 5 to about 100.] As used herein, when referring to the number of oxyalkylene units in a particular polyoxyalkylene compound, this number is not specifically stated. As long as it is understood, it means the average number of oxyalkylene units in such compounds.

[General Synthesis Method] The hydrocarbon group-substituted polyoxyalkyleneamine used in the present invention can be synthesized by the following general method and operation.
Even when typical or preferred operating conditions (eg, reaction temperature, time, reactant mole ratios, solvents, pressures, etc.) are noted, it is understood that other operating conditions can be used unless otherwise indicated. Should. Optimum reaction conditions will vary with the particular reactants and solvent used, but such conditions can be determined by one skilled in the art by routine optimization methods.

The hydrocarbon-substituted polyoxyalkyleneamine used in the present invention contains (a) a hydrocarbon-substituted polyoxyalkylene component and (b) an amine component.

A) Hydrocarbon-Substituted Polyoxyalkylene Component The hydrocarbon-substituted polyoxyalkylene polymer used for synthesizing the hydrocarbon-substituted polyoxyalkyleneamine used in the present invention is a monohydroxy compound,
That is, alcohols often referred to as polyoxyalkylene glycols, which are often "capped" with hydrocarbons, and should be distinguished from non-hydrocarbon terminated, i.e., uncapped, polyoxyalkylene glycols (diols). Hydrocarbon-substituted polyoxyalkylene alcohols are formed by adding a lower alkylene oxide, such as propylene oxide or butylene oxide, to a hydroxy compound ROH under polymerization conditions. Where R is a hydrocarbon group, as previously defined, capping the polyoxyalkylene chain. Preferred polyoxyalkylene polymers are C ₃ -C ₄
Which is derived from the oxyalkylene unit of For the production methods and properties of these polymers, see US Pat. Nos. 2,841,479 and 2,782,240 and Kirk Osmer's "Dictionary of Chemical Engineering" (Encycrop
edia of Chemical Technology, Vol. 19, p. 507)
Is disclosed. In the polymerization reaction, a single type of alkylene oxide, for example, propylene oxide, may be used, in which case the product is a homopolymer, for example, polyoxypropylene alcohol. However, copolymers are equally satisfactory, and random copolymers are readily synthesized by contacting a mixture of alkylene oxides, such as a mixture of propylene and butylene oxide, with a hydroxy-containing compound. Block copolymers of oxyalkylene units also provide satisfactory polyoxyalkylene units in the practice of the present invention.

The amount of alkylene oxide used in this reaction will generally depend on the number of oxyalkylene units desired in the product. Typically, the molar ratio of the alkylene oxide to the hydroxy-containing compound is about 5: 1.
From about 5: 1 to about 50: 1, more preferably from about 8: 1 to about 30: 1.

Alkylene oxides suitable for use in this polymerization reaction include propylene oxide and butylene oxide, for example, 1,2-butylene oxide (1,2-butylene oxide).
Epoxybutane) and 2,3-butylene oxide (2,3-epoxybutane). Preferred acetylene oxides are propylene oxide and 1,2-butylene oxide, both of which may be separate or a mixture thereof.

The hydrocarbon group R terminating the polyoxyalkylene chain generally contains from about 1 to about 30 carbon atoms, preferably from about 2 to about 20 carbon atoms, more preferably from about 4 to about 18 carbon atoms. And is generally derived from the monohydroxy compound ROH, which is the site of initiation of alkylene oxide addition in the polymerization reaction.
Such monohydroxy compounds are preferably aliphatic or aromatic alcohols having about 1 to about 30 carbon atoms, more preferably alkanols or alkyl phenols, and most preferably the alkyl substituent is about 1 to about 30 carbon atoms. Alkyl phenols that are from 1 to about 24 straight or branched chain alkyls. Preferred alkyl phenols include those in which the alkyl substituent contains from about 4 to about 16 carbon atoms. Particularly preferred alkyl phenols have an average of 4 when the alkyl group polymerizes propylene.
Propylene units, ie about 12 carbon atoms, commonly obtained as propylene tetramer. The resulting alkyl phenol is commonly referred to as tetrapropenyl phenol, or more commonly, dodecyl phenol. Preferred alkylphenol-derived polyoxyalkylene compounds can be referred to as alkylphenyl polyoxyalkylene alcohols or polyalkoxylated alkylphenols.

B) Amine Component As suggested above, the hydrocarbon-substituted polyoxyalkyleneamine used in the present invention contains an amine component. Generally, the amine component will contain, on average, at least about one basic nitrogen atom per molecule. The term "basic nitrogen atom" refers to a substance which can be titrated with a strong acid, such as a primary, secondary or tertiary amine nitrogen, which cannot be titrated with a strong acid, such as carbamyl such as -OC (O) NH-. It is distinguished from nitrogen. Preferably, at least one of the basic nitrogen atoms of the amine component is a primary or secondary amine nitrogen, more preferably at least one is a primary amine nitrogen.

The amine component of the hydrocarbon-substituted polyoxyalkyleneamine used in the present invention is preferably derived from ammonia, a primary alkyl or secondary dialkyl monoamine, or a polyamine having a terminal amino nitrogen atom.

The primary alkyl monoamines useful in synthesizing the compounds of the present invention contain one nitrogen atom and from about 1 to about 2
It contains zero carbon atoms, preferably contains about 1 to 6 carbon atoms, and most preferably contains 1 to 4 carbon atoms. Examples of suitable monoamines include N-methylamine, N-ethylamine, Nn-propylamine, N-isopropylamine, Nn-butylamine, N-isobutylamine, N-sec-butylamine, N-tert- Butylamine, Nn-pentylamine, N-cyclopentylamine, Nn-hexylamine, N-cyclohexylamine, N-octylamine, N-decylamine, N-dodecylamine, N-octadecylamine, N-benzylamine, N- (2-phenylethyl) amine, 2-aminoethanol, 3-amino-1-propanol, 2- (2
-Aminoethoxy) ethanol, N- (2-methoxyethyl) amine, N- (2-ethoxyethyl) amine and the like. Preferred primary amines are
N-methylamine, N-ethylamine and Nn-propylamine.

The amine component of the fuel additive used in the present invention may also be derived from secondary dialkyl monoamines. The alkyl groups of the secondary amines may be the same or different from each other and generally each comprise from about 1 to about 2
It contains 0 carbon atoms, more preferably about 1 to about 6 carbon atoms, and most preferably about 1 to about 4 carbon atoms. One or both of the alkyl groups may also contain one or more oxygen atoms.

Preferably, the alkyl group of the secondary amine is independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl, and 2-methoxyethyl. More preferably,
An alkyl group is methyl, ethyl or propyl.

Representative secondary amines which may be used in the present invention include N, N-dimethylamine, N, N-diethylamine, N, N-di-n-propylamine, N, N
-Diisopropylamine, N, N-di-n-butylamine, N, N-di-sec-butylamine, N, N-di-n
-Pentylamine, N, N-di-n-hexylamine,
N, N-dicyclohexylamine, N, N-dioctylamine, N-ethyl-N-methylamine, N-methyl-
N-n-propylamine, N-n-butyl-N-methylamine, N-methyl-N-octylamine, N-ethyl-N-isopropylamine, N-ethyl-N-octylamine, N, N-di (2-hydroxyethyl) amine,
N, N-di (3-hydroxypropyl) amine, N, N
-Di (ethoxyethyl) amine and N, N-di (propoxyethyl) amine. Preferred secondary amines are N, N-dimethylamine, N, N
-Diethylamine, and N, N-di-n-propylamine.

[0064] Cyclic secondary amines can also be used to form the additives used in the present invention. In such cyclic compounds, the alkyl groups, when taken together, form one or more 5- or 6-membered rings containing up to about 20 carbon atoms. Rings containing an amine nitrogen atom are generally saturated, but may be joined to one or more saturated or unsaturated rings. The ring may be substituted with a hydrocarbon group having about 1 to about 10 carbon atoms and may contain one or more oxygen atoms. Suitable cyclic secondary amines include piperazine, 4-methylpiperidine, pyrrolidine, morpholine, and 2,6-dimethylmorpholine.

Suitable polyamines can have a linear or branched structure, and can be cyclic or acyclic, or a combination thereof. Generally, the amine nitrogen atoms of such polyamines are separated from each other by at least two carbon atoms, ie, polyamines having an amino structure are not suitable. Polyamines also
It may contain one or more oxygen atoms and is usually present as an ether or hydroxyl group. Polyamines having a carbon to nitrogen ratio of about 1: 1 to about 10: 1 are particularly preferred.

In synthesizing the polyoxyalkyleneamine used in the present invention using a polyamine in which various nitrogen atoms of the polyamine are not geometrically equivalent, several substituted isomers are possible. Each of the possible isomers is also included in the present invention.

A particularly preferred group of polyamines for use in the present invention are polyalkylene polyamines including alkylenediamines. Such polyalkylene polyamines typically contain about 2 to about 12 nitrogen atoms and about 2 to about 40 carbon atoms, preferably about 2 to 24 carbon atoms. Preferably, the alkylene groups of such polyalkylene polyamines contain from about 2 to about 6 carbon atoms, more preferably, from about 2 to about 4 carbon atoms.

Examples of suitable polyalkylene polyamines include ethylenediamine, propylenediamine, isopropylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, dipropylenetriamine, dimethylaminopropylamine, diisopropylenetriamine, and diisopropylenetriamine. Mention may be made of butylenetriamine, di-sec-butylenetriamine, triethylenetetraamine, tripropylenetetraamine, triisobutylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, dimethylaminopropylamine, and mixtures thereof. Particularly preferred polyalkylene polyamines are those having the following general formula:

[0069]

Embedded image H ₂ N— (R ₃ —NH) _z —H

Wherein R ₃ is a linear or branched alkylene group having about 2 to about 6 carbon atoms, preferably about 2 to about 4 carbon atoms, most preferably about 2 to about 4 carbon atoms. 2,
That is, ethylene (—CH ₂ CH ₂ —); and z
Is an integer from about 1 to about 4, preferably about 1 or about 2]

Particularly preferred polyalkylene polyamines are ethylene diamine, diethylene triamine, triethylene tetraamine, and tetraethylene pentaamine. Most preferred are ethylene diamine and diethylene triamine, especially ethylene diamine.

[0072] Cyclic polyamines having one or more five or six membered rings are also contemplated for use in the present invention. Examples of such cyclic polyamine compounds include piperazine, 2-methylpiperazine, N- (2-aminoethyl) piperazine,
-(2-hydroxyethyl) piperazine, 1,2-bis- (N-piperazinyl) ethane, 3-aminopyrrolidine, N- (2-aminoethyl) pyrrolidine and the like can be mentioned. Preferred among the cyclic polyamines is piperazine.

Many of the polyamines suitable for use in the present invention are commercially available, and others can be synthesized by methods known in the art. For example, methods for synthesizing amines and their reactions are described in Sidgwick's "The Organic Chemistry of Nitrogen" (Clarendon Press, Oxford, 1966); and Noller's "Chemistry of Organic C".
ompouds, Sonders, Philadelphia, Second Edition,
1957); and Kirk-Othmer, encyclopedia of chemical engineering (second edition, especially Volume 2, pages 99-116).

C) Synthesis of Polyoxyalkyleneamine Substituted with Hydrocarbon Group As described above, the polyoxyalkyleneamine additive used in the present invention is obtained by directly or via an intermediate with a hydrocarbon-substituted polyoxyalkylene alcohol. , Ammonia, primary or secondary alkyl monoamines or polyamines.

The hydrocarbon-substituted polyoxyalkylene alcohol used to produce the polyoxyalkyleneamine used in the present invention is a generally known compound that can be synthesized by a conventional method. Suitable methods for synthesizing such compounds are described, for example, in US Pat.
Nos. 240 and 2,841,479, and U.S. Pat.
No. 882,945, the disclosure of which is incorporated herein by reference.

Preferably, the polyoxyalkylene alcohol is synthesized by contacting a metal salt of an alkoxide or phenoxide with about 5 to about 100 molar equivalents of an alkylene oxide, such as propylene oxide or butylene oxide, or a mixture of alkylene oxides.

Usually, a metal salt of an alkoxide or a phenoxide is prepared by reacting a corresponding hydroxy compound with a strong base such as sodium hydride, potassium hydride or sodium amide.
In an inert solvent such as toluene, xylene or the like, under substantially anhydrous conditions, at a temperature in the range of about -10 ° C to about 120 ° C for about 0.
It is synthesized by contacting for 25 to about 3 hours.

The metal salt of the alkoxide or phenoxide is generally not isolated, but reacts in situ with the alkylene oxide or alkylene oxide mixture to provide a polyoxyalkylene alcohol after neutralization. This polymerization reaction is usually carried out in a substantially anhydrous and inert solvent for about 3 hours.
The reaction is performed at a temperature of 0 ° C. to about 150 ° C. for about 2 to about 120 hours. Suitable solvents for this reaction include toluene and xylene. Usually, the reaction is carried out at a pressure sufficient to contain the reactants and solvent, preferably at atmospheric or room pressure.

The hydrocarbon-substituted polyoxyalkylene alcohol is then converted to the desired polyoxyalkylene amine by various methods known in the art. For example, the terminal hydroxy group of a hydrocarbon-substituted polyoxyalkylene alcohol may be first reacted with a suitable reagent such as methanesulfonyl chloride to be converted to a suitable leaving group such as mesylate, chloride or bromide. The resulting polyoxyalkylene mesylate or equivalent intermediate may then be converted to a phthalimide derivative by reaction with potassium phthalimide in the presence of a suitable solvent such as N, N-dimethylformamide. Next, the polyoxyalkylene phthalimide derivative is converted to the desired hydrocarbon-substituted polyoxyalkylene amine by reaction with a suitable amine such as hydrazine.

The polyoxyalkylene alcohol also
For example, see US Pat. No. 4,247,301 (Honen), the disclosure of which may be referred to, but the reaction with a suitable halogenating agent such as HCl, thionyl chloride or epichlorohydrin. After conversion to the corresponding polyoxyalkylene chloride, the chloride may be replaced by a suitable amine such as ammonia, primary or secondary alkyl monoamine or polyamine.

The hydrocarbon-substituted polyoxyalkyleneamine used in the present invention is described, for example, in US Pat.
No. 64 (Las, et al.) And No. 4,332,595 (Herbstmann, et al.), The disclosure of which can be referred to, but by the method commonly referred to as reductive amination, May be synthesized from a polyoxyalkylene alcohol.

In the reductive amination method, the hydrocarbon-substituted polyoxyalkylene alcohol is aminated with a suitable amine such as ammonia or a primary alkyl monoamine in the presence of hydrogen and a hydrogenation-dehydrogenation catalyst. The amination reaction is usually performed at a temperature in the range of about 160C to about 250C and a pressure of about 1000 to about 5000 psig, preferably about 1500 to about 3000 psig. Suitable hydrogenation-dehydrogenation catalysts may include those containing platinum, palladium, cobalt, nickel, copper or chromium, or mixtures thereof. In general,
An excess of the ammonia or amine reactant is used, for example, about a 5-fold to about 60-fold molar excess, and preferably about a 10- to about 40-fold molar excess of ammonia or amine.

When the reductive amination is carried out using a polyamine reactant, the amination may be carried out in its entirety, as described in European Patent Application Publication No. EP 0 781 793, issued Jul. 2, 1997. Although reference can be made, it is preferable to use a two-step method. According to this method, the polyoxyalkylene alcohol is first contacted with a hydrogenation-dehydrogenation catalyst at a temperature of at least about 230 ° C to provide a polymeric carbonyl intermediate, and then hydrogenated at a temperature of about 190 ° C or less. Reacting with a polyamine in the presence of a dehydrogenation catalyst to form a polyoxyalkylene polyamine adduct. The hydrocarbon group-substituted polyoxyalkyleneamine obtained by amination can be directly added to a hydrocarbon fuel.

[Fuel Composition] The fuel additive composition of the present invention is generally used in hydrocarbon fuels to prevent and suppress clogging of engine oil screens. Usually, the desired suppression of oil screen clogging is achieved by operating an internal combustion engine with a fuel composition containing the additive composition of the present invention. The proper concentration of additives needed to achieve the desired suppression of oil screen clogging will depend on the type of fuel used, the type of engine, the engine oil, operating conditions, and the presence or absence of other fuel additives.

The fuel additive compositions of the present invention are used in hydrocarbon fuels at concentrations generally ranging from about 20 parts per million to about 4000 parts by weight (ppm), preferably about 20 parts per million.
To about 2500 ppm.

With respect to the individual components, the hydrocarbon fuel containing the fuel additive composition of the present invention generally comprises about 10 to about 2000 ppm, preferably about 10 to about 500 ppm, of the Mannich condensate component, and a polyoxyalkyleneamine. About 10 to 2000 ppm, preferably about 10
About 1000 ppm. The weight ratio of polyoxyalkyleneamine to Mannich condensate is generally about 0.
5: 1 to about 12: 1, preferably about 0,1.
5: 1 to about 5: 1.

The fuel additive composition of the present invention has a boiling point of about 1
Formulated as a concentrate with an inert, stable, lipophilic (i.e., soluble in gasoline) organic solvent ranging from 50F to about 400F (about 65C to about 205C). it can. Preferably, an aliphatic or aromatic hydrocarbon solvent such as benzene, toluene, xylene or higher boiling aromatic hydrocarbon or aromatic thinner is used. Aliphatic alcohols containing about 3 to 8 carbon atoms, such as isopropanol, isobutyl carbinol and n-butanol, in combination with hydrocarbon solvents,
Suitable for use with the additives of the present invention. In concentrates, the amount of additive generally ranges from about 10 to about 70% by weight, preferably from 10 to 50% by weight, more preferably from 20 to 40% by weight.

In a gasoline fuel, other fuel additives may be used in combination with the additive composition of the present invention. Examples thereof include an oxygenating agent such as t-butyl methyl ether, methylcyclopentadienyl manganese triethanol. Mention may be made of anti-knock agents such as carbonyl, and other detergent dispersants such as hydrocarbon amines or succinimide.
In addition, antioxidants, metal deactivators, demulsifiers, and carburetor or fuel injector cleaners may be included. In diesel fuels, other well-known additives such as pour point depressants, flow improvers and cetane improvers can be used.

A fuel-soluble, non-volatile carrier liquid or oil may also be used with the fuel additive composition of the present invention. The carrier liquid is a chemically inert hydrocarbon soluble that substantially increases the non-volatile residue (NVR) or the non-solvent liquid component of the fuel additive composition without significantly contributing to the increase in octane requirements. It is a liquid medium. The carrier liquid may be natural or synthetic, such as mineral oil, refined petroleum, synthetic polyalkanes and alkenes, including hydrogenated and non-hydrogenated polyalphaolefins, and synthetic polyoxyalkylene-derived liquids. (For example, those described in US Pat. No. 4,191,537 [Lewis]), and polyesters (for example, US Pat. No. 3,756,793 [Robinson] and 5000044).
No. 8 [Bogel et al.], And those described in European Patent Application No. 356726 [issued on Mar. 7, 1990] and 382159 [issued on Aug. 16, 1990]).

It is believed that these carrier fluids serve as carriers for the fuel additive compositions of the present invention and also help control oil screen plugging as well as engine intake system deposits. When the carrier liquid is used in combination with the fuel additive composition of the present invention, the performance of suppressing clogging of the oil screen can be exhibited by a synergistic action.

The carrier liquid is generally used in an amount ranging from about 25 to about 5000 ppm by weight, based on the hydrocarbon fuel, preferably from 100 to 3000 ppm based on the fuel.
In the range. The ratio of carrier liquid to fuel additive preferably ranges from about 0.2: 1 to about 10: 1, and more preferably ranges from 0.5: 1 to 3: 1. When a carrier liquid is used in the fuel concentrate, the amount is generally about 20%.
To about 60% by weight, preferably in the range of 30 to 50% by weight.

[0092]

The following examples are presented to illustrate certain aspects of the present invention and its synthesis, and should not be construed as limiting the scope of the invention.

Example 1 Synthesis of dodecylphenoxypoly (oxypropylene) amine Dodecylphenoxypoly (oxypropylene) alcohol having an average molecular weight of about 1000 was reductively aminated with ammonia to give dodecylphenoxypoly (oxypropylene).
The amine was synthesized. Dodecylphenoxy poly (oxypropylene) alcohol is disclosed in US Pat. No. 4,191,537.
No. 2,782,240 and 2,841,479, and Kirk-Osmer's "Dictionary of Chemical Engineering"
(4th edition, vol. 19, p. 722, 1996), synthesized from dodecylphenol and propylene oxide. The reductive amination of dodecylphenoxy poly (oxypropylene) alcohol is described in US Pat.
No. 12364, No. 4609377 and No. 344002
No. 9 was carried out using the conventional technique described in each specification.

Example 2 Synthesis of Dodecylphenoxypoly (oxypropylene) amine Dodecylphenoxypoly (oxypropylene) alcohol having an average molecular weight of about 1400 was reductively aminated with ammonia to obtain dodecylphenoxypoly (oxypropylene).
The amine was synthesized. Dodecylphenoxy poly (oxypropylene) alcohol is disclosed in US Pat. No. 4,191,537.
Nos. 2,282,240 and 2,841,479, and Kirk-Othmer's "Dictionary of Chemical Engineering"
(4th edition, vol. 19, p. 722, 1996), synthesized from dodecylphenol and propylene oxide. The reductive amination of dodecylphenoxy poly (oxypropylene) alcohol is described in US Pat.
No. 12364, No. 4609377 and No. 344002
No. 9 was carried out using the conventional technique described in each specification.

Example 3 Synthesis of Dodecylphenoxypoly (oxybutylene) amine Dodecylphenoxypoly (oxybutylene) amine having an average molecular weight of about 1600 was reduced and aminated with ammonia to synthesize dodecylphenoxypoly (oxybutylene) amine. did. Dodecylphenoxy poly (oxybutylene) alcohol is disclosed in U.S. Pat. No. 4,191,537;
The compound was synthesized from dodecylphenol and butylene oxide according to the methods described in Nos. 782240 and 2841479, and Kirk-Osmer's Dictionary of Chemical Engineering (4th edition, volume 19, page 722, 1996). Reductive amination of dodecylphenoxy poly (oxybutylene) alcohol is described in US Pat.
It carried out using the prior art of each specification of No. 4609377 and No. 3440029.

Example 4 Synthesis of dodecylphenoxypoly (oxybutylene) poly (oxypropylene) amine Dodecylphenoxypoly (oxybutylene) which is a random copolymer of poly (oxyalkylene) alcohol and has an average molecular weight of about 1,598 Poly (oxypropylene) alcohol was reductively aminated with ammonia to synthesize dodecylphenoxy poly (oxybutylene) poly (oxypropylene) amine. Poly (oxyalkylene) alcohols are disclosed in U.S. Patent Nos. 4,191,537 and 27,822.
No. 40 and No. 2,841,479, and Kirk-Osmer's “Dictionary of Chemical Engineering” (4th edition, 19th edition).
Vol., P. 722, 1996) using butylene oxide and propylene oxide in a 75/25 weight / weight ratio from dodecylphenol. The reductive amination of a poly (oxyalkylene) alcohol is
It carried out using the prior art of each specification of U.S. Pat. Nos. 5,112,364, 4,609,377 and 3,444,0029.

Example 5 Synthesis of Mannich Condensate Glysopal 1000 polyisobutylene containing phenol at least 70% of a substance having a methylvinylidene terminal group (molecular weight: about 950, manufactured by BASF) in the presence of a BF ₃ -phenol catalyst ) To produce polyisobutylphenol, essentially mono-substituted in all para-positions. After neutralization and removal of BF ₃ and dilution with Exxon Aromatic 100 solvent, the diluted polyisobutylphenol has a hydroxyl number of 40.3 mg KO
H / g, and the nonvolatile residue content was 76.4%. After the alkylation step, the non-volatile residue contained 7% unconverted polyisobutylene.

3232 g of the above diluted polyisobutyl phenol was placed in a 5 L glass reaction vessel equipped with a stirrer, heating mantle, up-cooler, and Dane-Stark trap. Reactor temperature to room temperature (23 ° C)
Diethylenetriamine (Baker Chemical Company, purity 9
24.60 g (9.38%) was placed in the reactor and mixed with the diluted polyisobutylphenol until uniform. The reactor was then heated to 80 ° C. over 30 minutes in preparation for formalin injection.

Formalin was manufactured by Baker Chemical Company and contained 37.3% formaldehyde, 12% methanol, and 50.7% water. While continuing to heat to 91-93 ° C, formalin was injected over 150 minutes. Due to the exothermic reaction with formaldehyde, the temperature reached a maximum of 99 ° C. during this heating process. A temperature of 91-92 ° C was maintained for 60 minutes to complete the initial reaction.

Next, the reaction mixture was stirred at 150
C., while simultaneously reducing the pressure to 240 mmHg. Most of the water of reaction and some of the solvent were distilled off upward during the heating process. Except for the solvent stopped by the Dane-Stark trap, the remaining distilled solvent was continuously returned to the reactor. 144-151 ° C and 233-24
A final condition of 3 mmHg was maintained for 136 minutes to complete the reaction and water removal.

The reaction yield was 3508 g of a crude Mannich product. Upon cooling the contents of the reactor to 85 ° C., the Mannich crude sample gave a nonvolatile residue analysis of 82.0%. The Mannich crude was then diluted with 1940 g of Exxon Aromatic 100 solvent. Then, Celite Hyflo Supercell diatomaceous earth was supplied as
g and 16 g as a primer for the filter were used for filtration. The yield of clear and clear filtrate was 5265 g.
The filtered product had a nonvolatile residue content of 51.9% and a nitrogen content of 1.74%. Based on the assumption that the unconverted polyisobutylene in the non-volatile residue was not an active dispersant, the active ingredient content was 50%.

Example 6 Multi-cylinder Crankcase Hazardous Substance Screening Test The fuel additive composition of the present invention was tested on a laboratory multi-cylinder engine to evaluate the performance of suppressing oil screen clogging. evaluated.

A 1994 Ford 2.3 liter, single overhead cam, in-line four cylinder engine was used. Table 1 shows the main dimensions of the engine.
Each test was run for 80 hours (24 hours per day) in a prescribed test cycle, at the end of which the engine was disassembled,
The crankcase oil pickup tube and screen assembly were removed. Table 2 shows the engine operation cycle during the test. Next, the screen at the entrance of the oil pick-up pipe was changed to a coordinating research counsel
Evaluation was performed using the methodology described in Manual 12 (Sludge Evaluation Manual, CRC Manual 12), and the ratio of clogged areas was determined. A clean oil screen (free of sludge and debris) shows favorable crankcase performance. Large clogged oil screens exhibit poor crankcase performance.

As part of the Crankcase Hazard Screening Test, the engine was physically modified to increase the tendency to form sludge and varnish. Table 3 shows those physical changes. Also, as specified as part of the test method, the crankcase lubricating oil used in all test runs was Chevron 500 containing a commercially available antiwear agent.
N oil. No detergent or dispersant was added to the lubricating oil. All test runs were performed using the same base oil gasoline,
The base oil gasoline is manufactured by Philips Petrolium and is known as Philips "J" standard gasoline. Table 4 shows the basic properties of base oil gasoline.

[0105]

Table 1 Engine dimensions ─────────────────────── Inner diameter 9.60 cm Stroke 7.94 cm Exhaust capacity 2.30 liters Compression ratio 9. 50: 1───────────────────────

[0106]

[Table 2] Test cycle-3 stage test, total 80 hours 全── (20 loops, 240 minutes per loop) 1 step 2 steps 3 steps Duration per loop (min) 120 75 45 Speed (rpm) 2500 2500 800 Load (bhp) 33 33 − Coolant temperature (° F) 125 185 115 Oil temperature (° F) 155 210 115 Inlet air temperature (° F) 90 90 90 ─────────────────────────────── ─────

[0107]

[Table 3] Table 3 Physical changes of engine リ ン グ 0.080 inch ring gap Find rocker cover Camshaft baffle plate Addition of blow-through oil separator ───────────────────────

[0108]

Table 4 Fuel specifications ─────────────────────── Philips “J” standard fuel API specific gravity 54.2 (60 ° F) Specific gravity 0. 762 (60 ° F.) Sulfur 0.0114% by weight T10 127 ° F. T50 219 ° F. T90 328 ° F. Aromatic 42.0% by volume Olefin 15.3% by volume Paraffin + naphthene 42.7% by volume ──────────────────

The test compounds were mixed with the base oil fuel to the concentrations shown in Table 5. The ratio of oil screen clogging for each test sample is also reported in Table 5.

[0110]

[Table 5] Table 5 Ford 2.3-liter crankcase hazardous substance test試 料 Sample concentration% oil screen (ppma⁸Clogging ポ リ polyoxypropyleneamine¹ 200 100 Polyoxypropylene amine^Two 200 100 Polyoxypropylene amine^Three 200 95 Polyoxypropylene amine / Mannich product^Four 150/50 1 polyoxypropylene amine / Mannich product^Five 150/50 1 polyoxybutyleneamine⁶ 200 28⁹ Polyoxybutyleneamine / Mannich product⁷ 150/50 5──────────────────────────────────── ¹ Dodecylphenoxy synthesized as described in Example 1
Polyoxypropylene amine.^Two Dodecylphenoxy synthesized as described in Example 1
Polyoxypropylene amine.^Three Dodecylphenoxy synthesized as described in Example 2
Polyoxypropylene amine.^Four Dodecylphenoxy synthesized as described in Example 1
Example with polyoxypropylene amine 150 ppma
50 ppm of Mannich condensate synthesized as described in 5.
a mixture of a.^Five Dodecylphenoxy synthesized as described in Example 2
Example with polyoxypropylene amine 150 ppma
50 ppm of Mannich condensate synthesized as described in 5.
a mixture of a.⁶ Dodecylphenoxy synthesized as described in Example 3
Polyoxybutyleneamine.⁷ Dodecylphenoxy synthesized as described in Example 3
150 ppma of polyoxybutyleneamine and Example 5
50 ppma of a Mannich condensate synthesized as described in
Mixture.⁸ One million parts active ingredient.⁹ Average of 10 runs.

From the data in Table 5, it is clear that the combination of the polyoxyalkyleneamine and the Mannich condensate has a beneficial effect and provides a much better control of oil screen clogging than the polyoxyalkyleneamine component alone. It is.

[0112]

The fuel additive composition of the present invention comprising a combination of a Mannich condensate and a hydrocarbon-substituted polyoxyalkyleneamine can efficiently prevent and suppress clogging of an engine oil screen. Further, the fuel composition and the fuel concentrate containing the additive composition can significantly suppress the clogging of the engine oil screen.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Jacques E. Morris, Inventor, United States, California 94530, El Cerrito, Rifle Range Road 1348

Claims (34)

[Claims] 1. A fuel additive composition comprising: (a) (1) (1) a high molecular weight alkyl-substituted hydroxy aromatic compound having a number average molecular weight of about 300 to about 5000, (2) at least one And (3) an aldehyde, and the molar ratio of each reactant (1), (2) and (3) is from 1: 0.1 to 10: 0. And (b) a hydrocarbon-substituted polyoxyalkyleneamine represented by the following formula (I) or a fuel-soluble salt thereof: [Wherein, R is from about 1 to about 30 hydrocarbon group having carbon atoms; one of R ₁ and R ₂ is a methyl or ethyl, but the other is hydrogen, and R ₁ R ₂ is each independently selected for each —O—CHR ₁ —CHR ₂ — unit; A is amino, N-alkylamino having about 1 to about 20 carbon atoms in the alkyl group, Each alkyl group is an N, N-dialkylamino having from about 1 to about 20 carbon atoms, or a polyamine group having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms; and x Is
It is an integer of about 5 to about 100.] However, the weight ratio of the polyoxyalkyleneamine to the Mannich condensate is about 0.5: 1 to about 12: 1. 2. The fuel additive composition according to claim 1, wherein the alkyl group of the alkyl-substituted hydroxy aromatic compound has a number average molecular weight of about 400 to about 3000. 3. An alkyl group having a number average molecular weight of about 500 to
3. The fuel additive composition of claim 2, wherein the composition is about 2000. 4. The alkyl group has a number average molecular weight of about 700 to
4. The fuel additive composition according to claim 3, wherein the composition is about 1500. 5. The fuel additive composition according to claim 1, wherein the alkyl-substituted hydroxy aromatic compound is a polyalkylphenol. 6. The fuel additive composition according to claim 5, wherein the polyalkylphenol is polypropylphenol or polyisobutylphenol. 7. The fuel additive composition according to claim 6, wherein the polyalkylphenol is polyisobutylphenol. 8. The fuel additive composition according to claim 7, wherein the polyisobutyl phenol is derived from polyisobutene containing at least about 70% of the methylvinylidene isomer. 9. amine component of the Mannich condensation product is a compound represented by the following formula: ## STR2 ## _{H 2 N- (B-NH)} m -H [ wherein, B is about ten to several carbon atoms divalent alkylene And m is an integer from 1 to about 10]. 10. The fuel additive composition according to claim 9, wherein the alkylene polyamine is a polyethylene polyamine. 11. The fuel additive composition according to claim 10, wherein the polyethylene polyamine is diethylene polyamine. 12. The fuel additive composition according to claim 1, wherein the aldehyde component of the Mannich condensation product is formaldehyde, paraformaldehyde or formalin. 13. The fuel additive composition according to claim 1, wherein R is an alkyl group or an alkylphenyl group. 14. The fuel additive composition according to claim 13, wherein R is an alkylphenyl group. 15. The fuel additive composition according to claim 1, wherein one of R ₁ and R ₂ is methyl and the other is hydrogen. 16. The fuel additive composition according to claim 1, wherein x is an integer from about 5 to about 50. 17. The fuel additive composition according to claim 16, wherein x is an integer from about 8 to about 30. 18. The fuel additive composition according to claim 17, wherein x is an integer from about 10 to about 25. 19. The fuel additive composition according to claim 1, wherein A is an amino, N-alkylamino or polyamine group. 20. The fuel additive composition according to claim 19, wherein A is amino or N-alkylamino having about 1 to about 4 carbon atoms. 21. The fuel additive composition according to claim 20, wherein A is amino. 22. A having an amine nitrogen atom number of about 2 to about 1
20. The fuel additive composition according to claim 19, wherein the fuel additive composition is two polyamine groups having from about 2 to about 40 carbon atoms. 23. A is a polyamine group derived from a polyalkylene polyamine containing from about 2 to about 12 amine nitrogen atoms and from about 2 to about 24 carbon atoms.
3. The fuel additive composition according to item 2. 24. A polyalkylene polyamine having the formula: H ₂ N— (R ₃ —NH) _z —H wherein R ₃ is an alkylene group having about 2 to about 6 carbon atoms. And z is an integer from about 1 to about 4]. 25. The fuel additive composition according to claim 24, wherein R ₃ is an alkylene group having about 2 to about 4 carbon atoms. 26. The polyalkylene polyamine is ethylene diamine or diethylene triamine.
3. The fuel additive composition according to item 1. 27. The fuel additive composition according to claim 26, wherein the polyalkylene polyamine is ethylene diamine. 28. The fuel additive composition according to claim 1, wherein the weight ratio of the polyoxyalkyleneamine to the Mannich condensate is from about 0.5: 1 to about 3: 1. 29. A fuel composition comprising a major amount of a hydrocarbon oil having a boiling point in the range of the boiling range of gasoline or diesel fuel and a fuel additive composition comprising the following components in an amount effective to inhibit clogging of an engine oil screen. A fuel composition comprising: (a) (1) a high molecular weight alkyl-substituted hydroxyaromatic compound having a number average molecular weight of the alkyl group of about 300 to about 5000, (2) containing an amino group having at least one active hydrogen atom A Mannich condensate consisting of an amine, and (3) an aldehyde, and wherein the molar ratio of each reactant (1), (2) and (3) is 1: 0.1-10: 0.1-10; and (B) a hydrocarbon-substituted polyoxyalkyleneamine represented by the following formula (I) or a fuel-soluble salt thereof: [Wherein, R is from about 1 to about 30 hydrocarbon group having carbon atoms; one of R ₁ and R ₂ is a methyl or ethyl, but the other is hydrogen, and R ₁ R ₂ is each independently selected for each —O—CHR ₁ —CHR ₂ — unit; A is amino, N-alkylamino having about 1 to about 20 carbon atoms in the alkyl group, Each alkyl group is an N, N-dialkylamino having from about 1 to about 20 carbon atoms, or a polyamine group having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms; and x Is
An integer of about 5 to about 100], provided that the weight ratio of the polyoxyalkyleneamine to the Mannich condensate is about 0.1.
5: 1 to about 12: 1. 30. A composition comprising from about 10 to about 2000 pp.
m Mannich condensate, and about 10 to about 2000 pp
30. The fuel composition according to claim 29, comprising m polyoxyalkyleneamine. 31. The composition further comprises about 25 to about 50 by weight.
30. The fuel composition according to claim 29, comprising 00 ppm of a fuel-soluble, non-volatile carrier liquid. 32. The fuel composition according to claim 29, wherein the weight ratio of polyoxyalkyleneamine to Mannich condensate is from about 0.5: 1 to about 3: 1. 33. About 150 ° F. to 400 ° F. (about 65 ° C.
(A) a fuel concentrate comprising an inert, stable, lipophilic organic solvent having a boiling point in the range of from about 20 to about 205 ° C.) and from about 10 to about 70% by weight of a fuel additive composition comprising the following components: 1) a high molecular weight alkyl-substituted hydroxy aromatic compound having an alkyl group having a number average molecular weight of about 300 to about 5000; (2) an amine containing an amino group having at least one active hydrogen atom; and (3) an aldehyde. And a Mannich condensate wherein the molar ratio of each reactant (1), (2) and (3) is from 1: 0.1 to 10: 0.1 to 10; and (b) a compound represented by the following formula (I): A hydrocarbon group-substituted polyoxyalkyleneamine or a fuel-soluble salt thereof represented by the following formula: [Wherein, R is from about 1 to about 30 hydrocarbon group having carbon atoms; one of R ₁ and R ₂ is a methyl or ethyl, but the other is hydrogen, and R ₁ R ₂ is each independently selected for each —O—CHR ₁ —CHR ₂ — unit; A is amino, N-alkylamino having about 1 to about 20 carbon atoms in the alkyl group, Each alkyl group is an N, N-dialkylamino having from about 1 to about 20 carbon atoms, or a polyamine group having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms; and x Is
It is an integer of about 5 to about 100.] However, the weight ratio of the polyoxyalkyleneamine to the Mannich condensate is about 0.5: 1 to about 12: 1. 34. The fuel concentrate according to claim 33, wherein the fuel concentrate further comprises about 20 to about 60% by weight of a fuel oil-soluble, non-volatile carrier liquid.