JP2966927B2 - Automotive fuel additive composition and method for producing the same - Google Patents

Abstract

A motor fuel additive composition comprises a mixture of:(a) from 5-50 weight percent, based upon the total weight of the additive, of a detergent component selected from the group consisting of (i) at least one nonionic compound having a molecular weight in the range of 200-1500, (ii) a reaction product of a substituted hydrocarbon and an amino compound, and (iii) a polybutylamine or polyisobutylamine; and (b) a fuel conditioner component comprising (i) from 2-50 weight percent, based upon the total weight of the additive, of a polar oxygenated hydrocarbon compound and (ii) from 2-50 weight percent, based upon the total weight of the additive, of an oxygenated compatibilizing agent. The fuel conditioner component may additionally comprise a hydrophilic separant, an aromatic hydrocarbon, or mixtures thereof. The additive may also additionally comprise a carrier oil or fluidizer. The additive is prepared by mixing together the detergent and fuel conditioner components, and is advantageous in that the detergent and fuel conditioner components synergistically interact to reduce both fuel intake system deposit formation and combustion chamber deposit formation, thereby inhibiting engine ORI.

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to automotive fuel additive compositions and methods for making the same. In particular, the present invention provides: (a) a reaction product component which is a reaction product of a substituted hydrocarbon and an amino compound; and (ii) a detergent component selected from the group consisting of polybutylamine or polyisobutylamine. And (b) an automotive fuel additive composition comprising: (i) a polar oxygenated hydrocarbon compound; and (ii) a fuel conditioner component comprising: an oxygenated compatibilizer.

The present invention also relates to a process for producing an automotive fuel additive, comprising mixing the reaction product and a fuel conditioner component.

Incomplete combustion of hydrocarbonic automotive fuel during the internal combustion period
It is a matter of daily life, which results in the accumulation of carbon and other deposits in various devices, including fuel supply systems. Great efforts have been made to develop fuel additives that reduce or prevent deposit formation in engine fuel supply systems. Early so-called "first generation" additives primarily for vaporizer and injector cleaning include low molecular weight amines such as fatty amines, amides, amidoamines and isodazolines. A so-called "second generation" additive developed later,
Those relating to the cleaning of suction valves and vaporizers and injectors have been primarily based on polyolefin structures. For example, the use of polybutene succinimide as a fuel additive is described in US Pat. No. 3,443,918 (Kautsky
And US Pat. No. 3,172,892 (LeSeur et al.) And the use of polybutenamine as a fuel additive is disclosed in US Pat. No. 3,438,757 (Honnen et al.).

It is common to use such additives with petroleum based or synthetic carrier oils for effective deposit control. Useful petroleum base oils in this regard are the so-called Solvent Neutral Oils such as SNO-500 and SNO-600.
s) as well as relatively high viscosity naphthenic or paraffinic basestocks, including so-called top cylinder oils and the like. Practical synthetic oils include low molecular weight polypropylene and polyisobutylene, and polyalkylene oxides.

Although the above-mentioned additives have been found to be effective in reducing deposits in fuel supply systems, these additives, especially second generation additives, have been found to cause deposit formation in the combustion chamber in automotive fuels. . The presence of deposits in the combustion chamber greatly reduces engine operating efficiency for various reasons. First, deposit accumulation in the combustion chamber hinders heat transfer between the combustion chamber and the engine cooling system. This results in a high temperature in the combustion chamber and the terminal gas temperature of the incoming charge (en)
d gas temperature). After all, end gas auto-ignition
Which results in engine knock. In addition, deposit accumulation in the combustion chamber reduces the volume of the combustion zone, resulting in a compression ratio higher than the engine's design compression ratio.
This, in turn, results in significant engine knock. The knocking engine is not using combustion energy effectively. In addition, prolonged periods of engine knocking result in stress fatigue or wear in critical parts of the engine. The above phenomenon is a characteristic of gasoline engines. It can usually be overcome by using high octane gasoline to increase engine power. Therefore, it became known as the engine octane demand increase (ORI) phenomenon.

In view of the above, automotive fuels that reduce deposits in engine fuel intake systems and also prevent the formation of deposits in engine combustion chambers, thereby reducing or at least altering the composition of the deposits that tend to result in engine ORI Adopting additives in the composition is clearly advantageous. It is an object of the present invention to provide an automotive fuel additive useful in preventing both fuel supply system deposits and combustion chamber deposits. It is a feature of the present invention that the additive comprises a detergent component and a fuel conditioner component that reacts synergistically to reduce both fuel supply system and combustion chamber deposit formation. It is an advantage of the present invention to reduce both deposit formation in the fuel supply system and ORI associated with combustion chamber deposit formation.

Reducing deposits in the engine fuel supply system and reducing deposit formation in the engine combustion chamber;
It is another object of the present invention to provide a method for producing an automotive fuel additive thereby reducing engine ORI. It is another feature of the present invention to produce a mixture of such additives with a detergent component and a fuel conditioner component that reduces both the fuel delivery system deposit and the ORI associated with combustion chamber deposit formation.

The motor fuel additive of the Summary of the Invention of the present invention, (a) based on the total weight of the additive, (i) (A) formula R ₁ -X (I) (In the formula, R _1, 150-10,000 A hydrocarbyl group having a molecular weight of: X is selected from the group consisting of hydrogen, succinic anhydride, and succinic dibasic acid; and (B) a formula H- (NH- (A) _{m) n -Y-R 2 (} II) ( wherein, Y is O or NR _5, R ₅ is a hydrocarbyl radical having H or 1-30 carbon atoms; straight or branched having a is 1-30 carbon atoms A branched alkylene group; m is a value of 1-15; n is 0-
6 values; and R ₂ is H, a hydrocarbyl group and wherein R ₃ has a molecular weight of _{15-10,000 - ((Q) a (} T) b (Z) c) d - (III) ( wherein, R ₃ is H or a hydrocarbyl group having 1-30 carbon atoms, Q, T and Z are polyoxyalkylene moieties having 1-6 carbon atoms, a, b and c each have a value of 0-30, and d- is Selected from the group consisting of a homopolymeric or heteropolymeric polyoxyalkylene group represented by the following formula: (ii) a reaction product with an amino compound represented by the formula: Wherein R ₁₁ is isobutene and up to 20% by weight of n-
Butene-derived polybutyl or polyisobutyl groups, wherein R ₁₂ and R ₁₃ may be the same or different and are each hydrogen, aliphatic or aromatic hydrocarbon; primary or secondary, aromatic or aliphatic aminoalkylene group or A polyaminoalkylene group, a polyoxyalkylene group, or a hetaryl or heterocyclyl group, or a nitrogen atom to be bonded to form a ring in which a hetero atom may be further present); And (b) (i) based on the total weight of the additive, 2-50% by weight, an average molecular weight of 250-500 and an acid number of 25. -175 and a polar oxygenated hydrocarbon having a saponification value of about 30-250, and (ii) a solubility parameter of 2-50% by weight, based on the total weight of the additive. Moderator (moderat about 8.8-11.5)
e) Including a mixture of fuel conditioners containing an oxygenated compatibilizer with strong hydrogen bonding capacity.

The fuel conditioner component may additionally include a separant, such as glycol monoether, and an aromatic hydrocarbon, such as xylene, or xylene. The additive composition may additionally include a carrier oil or a fluidizer.

The present invention also relates to a process for producing an automotive fuel additive according to the invention, characterized in that the additive is obtained by mixing a detergent and a fuel conditioner component. In the automotive fuel additive of the present invention, the detergent and fuel conditioner components, when employed in the fuel composition, act synergistically to reduce fuel supply system deposit formation and improve engine performance. Engine ORI, and reduce combustion chamber deposit formation
Has the advantage of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the results of engine test stand experiments for various automotive fuel compositions, including automotive fuel compositions containing the additives of the present invention.

FIG. 2 is a plot of combustion chamber rating and intake valve deposit (mg) taken from the engine listed in FIG. 1 for various automotive fuel compositions, including automotive fuel compositions containing the additives of the present invention. The results of a test stand experiment are shown.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to automotive fuel additives and methods for their manufacture.

The additive comprises: (a) (i) a reaction product of a substituted hydrocarbon and an amino compound; (ii) a detergent component selected from the group consisting of polybutylamine or polyisobutylamine; and (b) a polar oxygenated carbon. A fuel conditioner comprising a hydride and an oxygenated compatibilizer.

If a reaction product detergent component is used,
The substituted hydrocarbon reactant used to prepare the reaction product has the formula R ₁ -X (I) wherein R ₁ is a hydrocarbyl group having a molecular weight of 150-10,000, preferably 400-5,000 And most preferably a polyalkylene group having a molecular weight of 600 to 1,500, and X is selected from the group consisting of halogen, preferably chlorine succinic anhydride, and succinic dibasic acid ).

In one preferred example, R ₁ -X is polyisobutenyl succinic anhydride. In another preferred example, R ₁ -X is chloropolyisobutylene.

Amino compound reactant used to produce the reaction product has the formula _{H- (NH- (A) m)} n -Y-R 2 (II) ( wherein, Y is, O or NR _5, where And R ₅ is H or 1
-30, preferably a hydrocarbyl group having 1-22 carbon atoms, A is a linear or branched alkylene group having 1-30, preferably 1-15 carbon atoms, and m is 1-
15, preferably 1-12, n is 0-6, preferably 0-5, and R ₂ is H, 15-10,000, preferably
Hydrocarbyl group having a molecular weight of 15-2,000, and wherein _{R 3 - ((Q) a} (T) b (Z) c) d - (III) ( wherein, R ₃ is H or 1-30, preferably 1 A hydrocarbyl group having -22 carbon atoms, Q, T and Z are polyoxyalkylene moieties having 1-6 carbon atoms, a, b and c each have a value of 0-30, and d is 1 -50, preferably 1-25), from the group consisting of homopolymeric or heteropolymeric polyoxyalkylene groups. ).

Various preferred examples of amino compound reactants of formula (II) are shown in Table I below.

In another preferred example, R ₂ is a homopolymeric or heteropolymeric polyoxyalkylene group as described above of formula (III). As used herein and in the claims, homopolymeric or heteropolymeric is a polyoxyalkylene compound, in the case of a homopolymeric compound, for example, ethylene oxide (EO),
Propylene oxide (PO) or butylene oxide (B
A polyoxyalkylene, such as O), which contains one repeating polyoxyalkylene moiety, usually having 1-6 carbon atoms, and in the case of heteropolymeric compounds, contains one or more repeating polyoxyalkylene moieties. . Thus, for example, in one example, R ₂ is represented by the formula R ₃ − ((EO)) _d − (where a = 1, b = 0, c = 0, Q =
Ethylene oxide, and R ₃ and d are as described above). In another example, R ₂ has the formula R ₃ -((EO) _a (PO) _b (BO) _c ) _d- (wherein, in formula (III), Q = ethylene oxide, T = propylene oxide, Z = Butylene oxide, and a,
b, c, d and R ₃ are as described above).

In yet another preferred example, the aforementioned amino compound reactant is selected from the group consisting of polyethylene polyamine, polypropylene polyamine, and mixtures thereof. In yet another preferred example, the polyamine is mono-alkylated.

The reaction product component is preferably a substituted hydrocarbon R ₁ −
X to the amino compound is 0.2: 1-20: 1, preferably 0.
It is prepared by reacting at a molar ratio of 5: 1-10: 1. The reaction product components are reacted under the reaction conditions (including, for example, reaction time, temperature, and reaction ratio), as is well known to those skilled in the art of preparing the amino-substituted hydrocarbon reaction product. Can be manufactured. Methods for producing the reaction products are described, for example, in US Pat. No. 3,172,892 (LeSeur et al.), US Pat. No. 3,438,757 (Honnen et al.), And US Pat.
3,443,918 (Kautsky et al.), Which are incorporated herein by reference.

The detergent compound has the formula Wherein R ₁₁ is a polybutyl or polyisobutyl group derived from isobutene and up to 20% by weight of n-butene;
And R ₁₂ and R ₁₃ may be the same or different, respectively, hydrogen, aliphatic or aromatic hydrocarbon, primary or secondary, aromatic or aliphatic aminoalkylene group or polyaminoalkylene group, polyoxyalkylene group, Or a heteroaryl or heterocyclyl group, or together with the nitrogen atom to which they are attached, forming a ring in which further heteroatoms may be present).

Compounds of general formula (IV) and methods for their preparation are disclosed in US Pat. No. 4,832,702 (Kummer et al.), Which is hereby incorporated by reference. The method compounds of general formula (IV) as disclosed in U.S. Patent No. 4,832,702, where the presence of suitable polybutenes or polyisobutenes rhodium or cobalt catalyst and CO and H _2, about 80-200 ° C., and CO /
The hydroformylation is carried out at an H ₂ pressure of less than 600 bar and the resulting oxo product is subsequently prepared under hydrogenation conditions by a Mannich reaction or an amination.
There, the amination reaction is advantageously at 80-200 ° C.
At a pressure below 600 bar, preferably at a pressure of 80-300 bar.

The fuel conditioner component used with the detergent component to make the additives of the present invention is preferably previously disclosed in U.S. Patent No. 4,753,661 (Nelson et al.), Which is hereby incorporated by reference. Include in. The fuel conditioner includes a polar oxygenated hydrocarbon compound and an oxygenated compatibilizer.

The polar oxygenated hydrocarbon portion of the fuel conditioner
The various organic mixtures resulting from the controlled oxidation of the petroleum liquor are signed with air. Often the air oxidation of these liquid distillates is from about 100 ° C to about 1
Manganese, copper, iron, cobalt, nickel, at a temperature of 50 ° C
Or organometallic catalysts, such as tin esters, or te
Performed with an organic catalyst such as rt-butyl peroxide. The result is a mixture of polar oxygenated compounds that fall into at least three categories: volatile, saponifiable and non-saponifiable.

The preferred polar oxygenated compounds for use in the present invention are characterized by three methods: molecular weight, acid number, and saponification number. Chemically, these oxidation products are mixtures of acids, hydroxy acids, lactones, esters, ketones, alcohols, anhydrides, and other oxygenated organic compounds. Suitable for the present invention are those having an average molecular weight of between about 250 and 500 and an acid number of about 25 and about
125 (ASTM-D-974), and a saponification value of about 30 to about 250
(ASTM-D-974-52). Preferably, the polar oxygenated compounds of the present invention have an acid number from about 50 to about 100 and a saponification number from about 75 to about 200.
Examples of polar oxygenated hydrocarbons within this preferred range include ALOX
400L (Alox Corporation, Niagara Fall, New York)
It is.

Suitable compatibilizers for use in the fuel conditioner component of the present invention are organic compounds having moderate to strong hydrogen bonding abilities with moderate solubility parameters. The solubility parameter, δ, based on the cohesive energy density, is the basic descriptor of the organic solvent that gives it its polarity. Simple aliphatic molecules of low polarity have a low δ of about 7.3 and water of high polarity have a high δ of 23.4. However, the solubility parameter is a first approximation of the polarity of the organic solvent. Also important for the generalized polarity, and thus the solvency, are the dipole moment and the hydrogen bonding capacity.
Symmetrical carbon tetrachloride and certain aromatic hydrocarbons with low gross dipole moment and low hydrogen binding capacity have a solubility parameter of about 8.5. In contrast, methyl propyl ketone has almost the same solubility parameters
8.7, but with a very strong hydrogen-bonding capacity and a constant dipole moment. Therefore, only one property of merit does not indicate the "polarity" of an organic compound.

In the practice of the present invention, the compatibilizer should have a solubility parameter of about 8.8 to about 11.5, and a moderate to high hydrogen-bonding capacity. Suitable classes of organic solvents are alcohols, ketones, esters, and ethers. Preferred compatibilizers are linear, branched and cycloaliphatic alcohols having 6 to 14 carbon atoms. Particularly preferred compounds as compatibilizers are hexanols, heptanols, octanols, nonyl alcohols, decanols, and dodecanols.

The fuel conditioner component of the present invention additionally comprises a hydrophilic separator which reduces the amount of water in the hydrocarbon fuel and thus improves combustion. Separants suitable for the practice of the present invention are ethers of glycols or polyglycols, especially monoethers. Monoethers are preferred over diethers for the purposes of the present invention.

Examples of such compounds that can be used are ethylene glycol, propylene glycol, trimethylene glycol, alpha butylene glycol, 1,3-butanediol, β-
Butylene glycol, isobutylene glycol, tetramethylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 2-methyl-2-ethyl-1,3 -Monoesters of propanediol and 2-ethyl-1,3-hexanediol.
Some monoethers include ethylene glycol monophenyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono- (n-butyl) ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-ethyl.
(N-butyl) ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monocyclohexyl ether, ethylene glycol monobenzyl ether, triethylene glycol monophenyl ether, butylene glycol mono- (p- (n-butoxy) phenyl) Ether, trimethylene glycol mono (alkylphenyl)
Ether, tripropylene glycol monomethyl ether, ethylene glycol mono-isopropyl ether,
Monophenyl ether of ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 1-butoxyethoxy-2-propanol, and polypropylene glycol, average molecular weight Is about 975 to 1075, and a monophenyl ether of polypropylene glycol, the polyglycol having an average molecular weight of about 400 to 450, and a monophenyl ether of polypropylene glycol, the polypropylene glycol having an average molecular weight of 975 to 1075. Such compounds include CELLOSOLVE, ethyl cellosolve, hexyl cellosolve, methyl carbitol (CARBITOL), butyl carbitol, dowanol (DOWANO)
L) Glycol ether, etc., are commercially available under trade names.

In the practice of the present invention, it has been found useful to include aromatic hydrocarbons or mixtures thereof in the fuel conditioner component of the present invention. Any aromatic hydrocarbon blend that is liquid at room temperature is suitable. Among these are benzene, toluene, three xylenes, trimethylbenzene, durene, ethylbenzene, cumene, biphenyl, dibenzyl and the like and mixtures thereof.
The preferred aromatic constituent is a commercial mixture of three xylenes. Because it is cheaper than pure xylene. As used herein and in the claims, the term "xylene" refers not only to the three specific xylene compounds, o-xylene, m-xylene and p-xylene, but also to benzene, toluene, and And aromatic "cuts" or distillates of aromatic hydrocarbons including naphthalene. Aromatic naphtha is also useful. Without being limited to any theory or process in using aromatic hydrocarbons, the presence of aromatic hydrocarbons in the conditioner has been found to promote clean and efficient combustion of the fuel. .

The composition of the present invention comprises petroleum base oil, mineral oil, molecular weight 500
Polypropylene compound having -3000, molecular weight 500-300
A polyisobutylene compound having 0 and polybutyl or polyisobutyl groups derived from polyisobutene and 20
Add an appropriate amount of carrier oil or fluidizer selected from the group consisting of polybutyl and polyisobutyl alcohols containing up to% by weight of n-butene, the corresponding carboxylate of polybutyl or polyisobutyl alcohol and mixtures thereof. May be included. Acceptable petroleum-based oils include so-called Solvent N
eutral Oils (SNO), such as SNO-500 and SNO-
Includes top cylinder oils and relatively high viscosity natural and synthetic naphthenic acid and paraffin base stock oils, including 600. Mineral oils that can be used include the so-called "light" mineral oils, that is, their petroleum,
It contains aliphatic or cycloaliphatic fractions having a viscosity of less than 0,000 SUS. Mixtures of hydrocarbon cuts may also be used in place of the base stock. The aforementioned polybutyl and polyisobutyl alcohols are disclosed in U.S. Pat. No. 4,859,210 (Fr
anz et al.) and are incorporated herein by reference. As used herein and in the claims, the terms "carrier oil" and "superplasticizer" may be interchanged, as will be readily appreciated by those skilled in the art.

A wide range of ratios are appropriate for the additive composition of the present invention when many of the above-described components are present. Hereinafter, the "useful range" and the "preferred range" are shown in% by weight based on the total weight of the additive composition.

Table 2 Components Useful Range Preferred Range Detergent Component 5-50 10-30 Polar Oxygenated Compound 2-50 5-25 Compatibilizer 2-50 5-25 Hydrophilic Separant 0-40 0-30 Aromatic Hydrocarbon 0 -80 0-30 Carrier Oil 0-80 0-60 The additive compositions of the present invention may be used in a wide range of hydrocarbon or modified hydrocarbon (eg, alcohol containing) fuels for various engines. Preferred automotive fuel compositions for use with the additive composition of the present invention are those intended to be used in spark ignition internal combustion engines. Such automotive fuel compositions, commonly referred to as gasoline basestocks, preferably comprise a mixture of hydrocarbons boiling in the gasoline boiling range, preferably about 90-450 ° F. This base fuel is straight, branched,
It may be composed of paraffins, chloroparaffins, olefins, aromatic hydrocarbons, and mixtures thereof. This base fuel is, among others, straight run naphtha,
It may be derived from polymer gasoline, natural gasoline, or catalytically cracked or hot cracked hydrocarbons and catalytically rehomed stock. The fuels include synthetic hydrocarbons, ethers such as methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), alcohols such as methanol, ethanol, TBA, and other functional organic compounds; For example, ketones, esters and the like can also be included. The composition and octane number of the base fuel is not critical and any conventional automotive base fuel may be employed in the practice of the present invention. In addition, the automotive fuel composition may additionally include an anti-knock compound (eg, tetraethyl lead), an anti-icing additive, an upper cylinder lubricant, a carburetor detergent rust inhibitor, a demulsifier, a deodorant, and the like. Other additives commonly employed in various automotive fuels can be included.

The invention has been described above and will be described in the following examples. However, these embodiments do not limit the invention, and may be implemented in other systems by other means.

Example 1 (Comparative Example) Two cars (Ford Escort and Chevrolet Cavalier) were run without detergent additives and the gasoline was 7000 miles (30 miles) using the same unleaded base gasoline with (RON + MON) / 2 octane number = 87. % City driving, 70% highway driving). Prior to the start of the test, the engine was disassembled and its combustion chamber was thoroughly cleaned. After that,
Reassembled with new spark plugs and new valves.

After a 7000 mile drive test, the engine was disassembled again and the deposits collected on the tulip of the intake valve and in the combustion chamber were collected and weighed. The results are summarized below.

Example 2 (Comparative Example) The same test as performed in Example 1 was repeated. However, a lead-free base fuel containing a recommended level of a separate commercially available fuel detergent additive package was used for each vehicle. After 7,000 miles, the following results were obtained:

The above results indicate that, while the commercial additives A and B improve the suction valve cleaning compared to Example 1, the combustion chamber deposit formation actually increased, and thus the engine ORI was disadvantageously enhanced. Is shown.

Example 3 (Comparative Example) The same test as that performed in Example 1 was performed. However, as disclosed in U.S. Pat. No. 4,753,661, Polar Mol
DurAlt Fuel Cond from ecular Corp. (Saginaw, Mi)
An unleaded base fuel containing 500 ppm of a fuel conditioner component of the present invention, available under the trade name itioner, was used. The following results were obtained.

Example 4 (Invention) The same test was performed as in Example 1. However, each additive (A or B) of Example 2, plus 500 ppm
Polar Molecu under the trade name DurAlt Fuel Conditioner
A lead-free base fuel containing the fuel conditioner component of the present invention, available from lar Corp. (Saginaw, Mi), was used for each vehicle. The following results were obtained.

The above results show that the additive compositions of the present invention, when employed in automotive fuel compositions, tend to reduce both intake valve deposits and combustion chamber deposits, and thus engine ORI. These results are unexpected, and the use of Additives A and B without the DurAlt fuel conditioner (as in Example 2) resulted in a larger (i.e., 3-4 times larger) combustion chamber deposit formation. And thus show a greater ORI trend. Thus, the combination of detergent and fuel conditioner components in the additive composition of the present invention serves to synergistically reduce both suction valve deposit formation and combustion chamber deposit formation.

Example 5 (Invention) The same test as performed in Example 1 was performed. However, each additive (A or B) as in Example 2 plus 30
A lead-free base fuel containing 0 ppm and 100 ppm DurAlt fuel conditioner, respectively, was used for each vehicle. The following results were obtained.

The above results also indicate that the additive compositions of the present invention, when used in automotive fuel compositions, tend to reduce both intake valve deposits and combustion chamber deposits, and thus reduce engine ORI. . These results are also unexpected, and using additives A and B without the DurAlt fuel conditioner (as in Example 2) would result in a larger (i.e. 2-3 times) combustion chamber deposit. Shows formation and therefore a greater ORI tendency.
Thus, the combination of detergent and fuel conditioner in the additive composition of the present invention acts synergistically to reduce both suction valve deposit formation and combustion chamber deposit formation.

Example 6 (Comparative Example) The same test as that performed in Example 1 was performed on car # 2. However, vehicle # 2 is additive package B plus 500 ppm US Pat. No. 4,548,616 (Sung
Etc.) were used with a lead-free base fuel having the same commercially available additives. The additive was a poly (oxyethylene) (oxypropylene) polyol.
This additive is available from BASF Wyandotte Corp under the PLURONIC series trade name. The following results were obtained.

The above results indicate that additive package B plus poly (oxyethylene) poly (oxypropylene) polyol (PL
URONIC L-31) is responsible for the formation of the combustion chamber deposit,
The control of the engine ORI is shown to be less effective than the additives of the present invention exemplified in Examples 4 and 5.

Example 7 (Invention) A Honda Acort, I-4 engine, 2-barrel carburetor equipped, running 64.550 miles was initially driven on leaded gasoline with a commercially available additive and found to have knocking problems. The car was then combined with an additive composition of the present invention, such as an additive composition comprising Additive B listed in Example 2 (ie, 350 ppm polybutene anomi type additive and
The fuel was run 2000 miles on a fuel containing an additive composition containing 600 ppm top cylinder oil) + 500 ppm DurAlt FC. The knocking problem has disappeared as a whole, and thus has shown a clear decrease in the engine ORI of this car. This embodiment illustrates the utility of the present invention in a so-called "clean-up" application, where the use of the present invention improves the performance of an engine that has already exhibited engine ORI.

Additional experimental results were obtained using the ES6500 Honda generator engine test system. Same load (1500 and 2500
Employing the same engine system of watt electric resistance hot water heater, SAE magazine No. 892121 (International Fuel and Lubricants Conference, submitted to Baltimore, Md, Sept, 1989), "Suction Valve Stykinis" And the development of a gasoline additive screening test for deposit levels ", incorporated herein by reference, with the following amendments.

The engine was disassembled and prepared for testing. The inlet valve was then washed with a gum sorbent consisting of a mixture of 1/3 acetone, 1/3 toluene, and 1/3 methanol to remove lubricating oil on the valve. The valve was then placed in a desiccator for at least one hour and then weighed to an accuracy of 0.1 mg on a balance prior to engine assembly. The combustion chamber and ports were cleaned with a suitable wire brush, and the top of the piston was also cleaned. A clean cylinder head was reassembled, installed on the engine, and reassembled for the rest of the engine. Oil and oil filters were changed prior to testing.

A fuel composition to be tested was prepared and injected into a fuel tank. I started the engine, idled for 30 seconds and warmed up. The engine was then run at 1500 watt load for 2 hours. At the end of the two hours, the generator load, coolant in / out temperature, oil temperature, exhaust temperature of cylinders 1 and 2, and manifold vacuum were recorded. The engine was then run for another 2 hours under a 2500 watt load.
At the end of the two hours, the above data was recorded again. The above-described 4-hour test driving method was operated for 16 hours a day with the engine operated for 5 days (with fuel supplied) for a total of 80 hours.
At the end of the 80 hours, the generator fuel tank was drained and added to the remaining fuel mix for operation. The total amount of residual fuel was measured and the amount of fuel used during 80 hours of operation was calculated.

After 80 hours of operation, the engine was disassembled and the cylinder head, camshaft, and rocker arm assembly were removed. The amount of deposit on the inhalation system consisting of the carburetor throttle plate, intake manifold, head runner, paste port and intake valve is determined by the coordinating research counsel (CRC) rating manual N known to those skilled in the art.
o.16, Atlanta, Ga, 1987 ("CRC rating")
Was graded using the method described in The combustion chamber and piston top were similarly graded using a CRC rating system. Grading, bulb weighing, and photography were performed as follows. The piston top, cylinder head, combustion chamber, hand runner, intake manual and throttle plate were all graded first and photographed. The combustion side of the suction valve was subsequently cleaned and the suction valve was carefully removed without damaging the deposits collected thereon. The valve stem was wiped with gum sorbent to remove the lubricating oil and then photographed.
The valve was then placed in a desiccator for one hour, then removed and weighed immediately. Weight is 0.1mg
Recorded. Place the valve in the desiccator for another 0.
Returned for 5 hours and weighed again. This process was repeated until the valve weighing was within 0.5 mg. The valve was then washed with a gum sorbent and a wire brush and placed in a desiccator until final weighing was ready. The engine was then reassembled with a new set of intake valves and engine operation was repeated.

Base fuel compositions obtained from Sun Refining and Marketing Company were used in all of the following examples. The analysis of the base fuel composition was as follows. Item Result API Gravity ASTM D287 56.1 Research Octane No., ASTM D2699 95.2 Motor Octane ASTM D2700 84.2 Sensitivity (RM) 11.0 Octane (R + M) / 2 89.7 Reid Vapor Pressure psi ASTM D323 Automation 9.1 Distillation ASTM D86 Automation IBP 93 10% Evaporation 131 50% Evaporation 220 90% Evaporation 336 FBP 411 Hydrocarbon composition% by volume, ASTM D1319 Aromatic 30.4 Olefin 17.1 Saturated 52.5 This base fuel composition, no additives, was tested on each of two Honda engine systems. The result of the comparison was obtained. Intake valve deposit weighing (milligrams) and combustion chamber grading (according to the CRC method described above) were obtained for each engine as follows.

Example 8 (Comparative example) Various fuel compositions, including fuel compositions including the additive compositions of the present invention, were tested on a Honda generator engine using the techniques described above to obtain suction valve deposit measurements and combustion chamber grading measurements. The test results are shown below.

Example 9 Base fuel composition from Sun Refining and Marketing Company and additionally the following additives Fuels Nos. I-VII were used according to the amount of intake valve deposit (mg) and as described in FIG.
C) Graded for grading. As is clear from FIG. 2 plotting the data shown in FIG.
II, V and VII (ie, the fuel composition contains the additive of the present invention) have both a combustion chamber rating (ie, a high CRC rating) and a suction valve deposit (ie, a low mg deposit value on the suction valve). It showed excellent characteristics.

It should be understood that the terms and expressions used in this specification are for explanation, not for limitation. It is to be understood that these descriptive terms and expressions are not intended to exclude equivalents, and that various modifications are possible within the scope of the claims of the present invention.

Continuation of front page (72) Inventor Nelson Otis L. Jr., United States, 49653, Michigan, Lake Lilanau, Country Line 643, Box 644, Route 1 (No Address) (58) Fields surveyed (Int. Cl. ⁶ , DB name) C10L 1/18 C10L 1/22 C10L 1 / 14 WPI / L (QUESTEL) EPAT (QUESTEL)

Claims (18)

(57) [Claims] (1) (a) (i) (A) Formula R ₁ -X (I) wherein R ₁ is a hydrocarbyl group having a molecular weight in the range of 150-10,000 and X is halogen, succinic a substituted hydrocarbon represented by chosen) from anhydrides and Sukushinikku group consisting of dibasic acid, (B) formula _{H- (NH- (A) m)} n -Y-R 2 (II) ( wherein, Y is O or NR _5, R ₅ is a hydrocarbyl radical having H or 1-30 carbon atoms; a is linear or branched alkylene group having 1-30 carbon atoms; the value of m is 1-15; the n 0 −
6 values; and R ₂ is H, a hydrocarbyl group having a molecular weight in the range of 15-10,000, and the formula _{R 3 - ((Q) a} (T) b (Z) c) d - (III) ( wherein , R ₃ is H or 1-30 hydrocarbyl group having carbon atoms, Q, T and Z are polyoxyalkylene moieties having 1-6 carbon atoms, a, b, c are respectively 0-30
And d has a value in the range of 1-50), and is selected from the group consisting of homopolymeric or heteropolymeric polyoxyalkylene groups), and a reaction product with an amino compound represented by the formula: (Ii) Formula Wherein R ₁₁ is isobutene and up to 20% by weight of n-
A polybutyl or polyisobutyl group derived from butene, and R ₁₂ and R ₁₃ are the same or different and each represents hydrogen, an aliphatic or aromatic hydrocarbon, a primary or secondary, an aromatic or aliphatic aminoalkylene group or a polyaminoalkylene group; , A polyoxyalkylene group or a hetaryl or heterocyclyl group, or a nitrogen atom to which they are bonded to form a ring in which a hetero atom may be further present). 5-50% by weight of the detergent component, based on the total weight of the additive, selected from the group; and (b) (i) 2-50% by weight, based on the total weight of the additive
Average molecular weight 250-500, acid number 25-175, and saponification number 3
A polar oxygenated hydrocarbon having 0-250, and (ii) 2-50% by weight, based on the total weight of the additive, a solubility parameter of about 8.8-11.5 and moderate to strong hydrogen-
An automotive fuel additive composition comprising a mixture of fuel conditioner components comprising an oxygenating compatibilizer having binding ability. 2. The composition of claim 1 wherein the molar ratio of the substituted hydrocarbon R ₁ -X to the amino compound is from 0.2: 1 to 20: 1. 3. The composition according to claim 1, wherein R ₁ -X is chloropolyisobutylene or polyisobutenyl succinic anhydride. 4. A compound according to claim 1, wherein R ₂ is H, a hydrocarbyl group having a molecular weight in the range of 15-2000, and a polyoxyalkylene group of the formula (III), wherein R ₃ is H or a hydrocarbyl group having 1-22 carbon atoms. , Q, T and Z are polyoxyalkylene moieties having 1-6 carbon atoms, a, b, c and d
Is a value in the range of 1-25, Y is O or NR ₅ (where R ₅ is H
Or a hydrocarbyl group having 1-22 carbon atoms), A
Is a linear or branched alkylene group having 1-15 carbon atoms, m is a value in the range of 1-12, and n is a value in the range of 0-5). . 5. The composition of claim 1, wherein said amino compound of formula (II) is selected from the group consisting of polyethylene polyamines, polypropylene polyamines, and mixtures thereof. 6. The composition according to claim 1, wherein said compatibilizer is an alcohol containing 3 or more carbon atoms. 7. A composition according to claim 1, wherein said fuel conditioner component additionally comprises 0-40% by weight, based on the total weight of the additive, of a hydrophilic separator. 8. The fuel conditioner component further comprising:
The composition according to claim 1, comprising 0-80% by weight of aromatic hydrocarbon based on the total weight of the additive. 9. An amount of 0-80% by weight, based on the total weight of the additive,
Petroleum-based oils, mineral oils, polypropylene compounds having a molecular weight in the range of 500-3000, polyisobutylene compounds having a molecular weight in the range of 500-3000, polyoxyalkylene compounds having a molecular weight in the range of 500-3000, and polyisobutene and 20 Up to% by weight of polybutyl or polyisobutyl alcohols containing n-butene-derived polybutyl or polyisobutyl groups-the corresponding carboxylate of said polybutyl or polyisobutyl alcohol;
The composition of claim 1, further comprising a carrier oil selected from the group consisting of: and a mixture thereof. 10. (a) (i) (A) Formula R ₁ -X (I) wherein R ₁ is a hydrocarbyl group having a molecular weight in the range of 150-10000, and X is halogen, succinic a substituted hydrocarbon represented by chosen) from anhydrides and Sukushinikku group consisting of dibasic acid, (B) formula _{H- (NH- (A) m)} n -Y-R 2 (II) ( wherein, Y is O or NR ₅ , R ₅ is H or a hydrocarbyl group having 1 to 30 carbon atoms; A is a linear or branched alkylene group having 1 to 30 carbon atoms; m is a value of 1 to 15; 0
-6 value; and R ₂ is H, a hydrocarbyl group having a molecular weight in the range of 15-10000, and, wherein _{R 3 - ((Q) a} (T) b (Z) c) d - (III) ( wherein Wherein R ₃ is H or a hydrocarbyl group having 1-30 carbon atoms, Q, T and Z are polyoxyalkylene moieties having 1-6 carbon atoms, and a, b and c are each 0-30.
And d has a value in the range of 1-50), which is selected from the group consisting of homopolymeric or heteropolymeric polyoxyalkylene groups). And (ii) Wherein R ₁₁ is isobutene and up to 20% by weight of n-
A polybutyl or polyisobutyl group derived from butene, and R ₁₂ and R ₁₃ are the same or different and each represents hydrogen, an aliphatic or aromatic hydrocarbon, a primary or secondary, an aromatic or aliphatic aminoalkylene group or a polyaminoalkylene group; Or a polyoxyalkylene group or a hetaryl or heterocyclyl group, or a nitrogen atom to which they are bonded to form a ring in which a hetero atom may be further present), a polybutylamine or a polyisobutylamine represented by 5 based on the total weight of the additives selected from the group
(B) (i) 2-50% by weight based on the total weight of the additives
Average molecular weight 250-500, acid number 25-175, and saponification number 3
A polar oxygenated hydrocarbon having 0-250, and (ii) 2-50% by weight, based on the total weight of the additive, of a solubility parameter of about 8.8-11.5 and moderate to strong hydrogen.
A method for producing an automobile fuel additive, comprising mixing an oxygenated compatibilizer having binding ability. 11. The method of claim 10, wherein the molar ratio of the substituted hydrocarbon R ₁ -X to the amino compound is from 0.2: 1 to 20: 1. 12. The method according to claim 10, wherein R ₁ -X is chloropolyisobutylene or polyisobutenyl succinic anhydride. 13. R ₂ is H, a hydrocarbyl group having a polyoxyalkylene group (wherein, R ₃ is H or 1-22 carbon atoms of hydrocarbyl groups having a molecular weight in the range of 15-2000, and the formula (III) , Q, T, and Z are polyoxyalkylene moieties having 1-6 carbon atoms, a, b, values in the range of c and d is 1-25, Y is O or NR ₅ (wherein R ₅ is H or A hydrocarbyl group having 1-22 carbon atoms),
A method according to claim 10, wherein A is a straight or branched alkylene group having 1-15 carbon atoms, m is a value in the range 1-12, and n is a value in the range 0-5). . 14. The method of claim 10, wherein said amino compound of formula (II) is selected from the group consisting of polyethylene polyamines, polypropylene polyamines, and mixtures thereof. 15. The composition according to claim 10, wherein said compatibilizer is an alcohol containing three or more carbon atoms. 16. The method of claim 10, wherein said fuel conditioner component additionally comprises 0-40% by weight, based on the total weight of the additive, of a hydrophilic separator. 17. The method according to claim 10, wherein said fuel conditioner component additionally comprises from 0 to 80% by weight of aromatic hydrocarbon, based on the total weight of the additive. 18. 0-80% by weight based on the total weight of the additives
Petroleum-based oils, mineral oils, polypropylene compounds having a molecular weight in the range of 500-3000, polyisobutylene compounds having a molecular weight in the range of 500-3000, polyoxyalkylene compounds having a molecular weight in the range of 500-3000, and polyisobutene And up to 20% by weight of polybutyl and polyisobutyl alcohols containing polybutyl or polyisobutyl groups derived from n-butene, the corresponding carboxylate of said polybutyl or polyisobutyl alcohol, and mixtures thereof. 11. The method of claim 10, additionally comprising.