JPH03265689A - Fuel oil additive composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in capability of cleaning a fuel inlet system and a combustion chamber by using an amine(oxide) and a specified compound as the constituents. CONSTITUTION:The title composition is obtained by mixing 1-50wt.% amine(oxide) which has a 3-18C alkyl branch, alkyl having a total number of carbon atoms including those of the branch of 9 to 37, and at least one 2-4C oxyalkylene group (e.g. 2-tetradecyloctadecyloxypropylamine); 1-30wt.% compound of formulas I, II or III (wherein R<1> to R<5> are each 15-100C alkyl or alkenyl; A is a group of formula IV or V; p is 1 to 3; q is 0 to 5; X1 is H or of formula VI; X2 is H or a group of formula VII; X3 is H, 15-100C alkyl or alkenyl), having a molecular weight of 700 to 5,000; and 50-98wt.% mineral oil or synthetic oil [e.g. (hydrogenated) polybutene having a molecular weight of 400 to 2,000]. 0.1-50,000ppm of this composition is incorporated into fuel oil.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fuel oil additive composition, particularly a gasoline additive composition. The present invention relates to a fuel oil additive composition.

In the present invention, fuel oil refers to fuel used in internal combustion engines, such as gasoline, diesel light oil, and heavy oil.

[Prior Art and Problems to be Solved by the Invention] When deposits such as sludge and deposits are formed in the fuel system and combustion chamber of an internal combustion engine, the engine performance deteriorates and exhaust gases are adversely affected.

Fuel detergents, particularly gasoline detergents, are added to gasoline for the purpose of removing and preventing deposits from adhering to gasoline intake systems such as carburetors and intake valves, and for purifying the inside of combustion chambers. Deposits formed on intake valves and intake ports cause a reduction in engine output, deterioration of drivability, and an increase in exhaust gas.

In recent years, engines have become increasingly sophisticated and, as a result, more sensitive to such deposits.

Among these, deposits on intake valves have recently become a big problem, especially in Japan, where the number of passenger cars equipped with electronically controlled injection devices has been increasing. The electronically controlled fuel injection system precisely controls the gasoline mixture,
It is effective not only for improving engine performance but also for improving fuel efficiency and exhaust gas. However, when deposits adhere to the intake valve, gasoline injected from the injection device hits the deposits, disrupting control of the gasoline mixture, and as a result, drivability is adversely affected.

The present inventors have proposed (a) a fuel additive with a carbon number of 3 to 18 as superior in the cleanliness of the fuel intake system and combustion chamber than in the prior art;
an amine or amine oxide having an alkyl group having an alkyl branch and having an alkyl group having 9 to 37 carbon atoms including the branched portion, and (b) having one or more oxyalkylene groups having 2 to 4 carbon atoms; Alternatively, they discovered a blend of this amine or amine oxide and mineral oil or synthetic oil, and have already filed a patent application (Japanese Patent Application No. 193757/1999). This invented product has the ability to remove deposits that accumulate on the intake valves of gasoline car engines under high concentrations of additives (1000~
10,000 ppIll), but the ability to maintain the cleanliness of the intake valve at low concentrations (250 ppIll or less) was unsatisfactory. When the cause of this was investigated, it was found that the heat resistance at high temperatures was slightly inferior. The temperature of the intake valve is said to be around 200"C to around 350"C, and if the additive is at a low concentration and reaches a high temperature of 250"C or higher, depending on the conditions, the additive may thermally deteriorate and lose its cleanliness. was considered.

[Means to solve the problem]

In order to solve the second problem of the prior art, the present inventors have arrived at the present invention as a result of intensive research.

That is, the present invention provides: (A) (a) having an alkyl branch having 3 to 18 carbon atoms;
(B) an amine or agone oxide having an alkyl group having 9 to 37 carbon atoms including the branched portion, and (b) one or more oxyalkylene groups having 2 to 4 carbon atoms; The following general formula (1), (II) or (I[I)H (wherein R1 is an alkyl group or alkenyl group having 15 to 100 carbon atoms, A is 10NH→CH2h−+−NH− or →NH →CH
t→-NH-Co-NH+ (CHz+TNH, p is an integer of 1 to 3, q is an integer of 0 to 5, H represents an alkyl group or alkenyl group of ~100.) (In the formula, R3 is the number of carbon atoms 15 to 100 alkyl group or R4 is an alkyl group or alkenyl group having 15 to 100 carbon atoms, p is an integer of 1 to 3, and q is an integer of 0 to 5.) R'+NHnC) IJy-h-NH- Xs −(In
) (wherein, R5 is an alkyl group or alkenyl group having 15 to 100 carbon atoms, χ is H or an alkyl group or alkenyl group having 15 to 100 carbon atoms, p is an integer of 1 to 3, and q is O-
), which represents an integer of 5, and has a molecular weight of 700 to 50.
The present invention provides a fuel oil additive composition characterized in that it contains a compound of No. 00.

The component (A) used in the present invention has 3 to 18 carbon atoms.
As an amine or amine oxide having an alkyl branch, having an alkyl group having 9 to 37 carbon atoms including this branched part, and (b) having one or more oxyalkylene groups having 2 to 4 carbon atoms. For example, the following general formula (I
Examples include compounds represented by L (2) or (3).

[In the formula, Rr and Rz are hydrocarbon residues having 3 to 18 carbon atoms, and the sum of the carbon numbers of R5 and R7 is 8 to 36.

n is O or an integer of 1 to 4.

3 Y represents an amine, amine oxide, side residue, or min oxide residue represented by the formula →B O)'y-R→E-N+-t-R4 (here, B has 2 to 4 carbon atoms) alkylene group, - is an integer from 0 to o, R is -, -CH2CO
A group selected from NH-, -CHzCH(OR)-, -CHzCH-, E is - or an alkylene group having 1 to 4 carbon atoms,
R3 and R4 are H, or an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, or an aminoalkyl group, and 1 is 1 or 2). ] As Rr and Rz in formulas (1) to (3), a straight chain hydrocarbon group or a branched hydrocarbon group is used. Examples of the straight chain hydrocarbon group include n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-hebutyl group, n-octyl group, n-nonyl group, n-decyl group. ,n
-undecyl group, n-dodecyl group, n-)lysosyl group,
Examples include n-tetradecyl group, n-pentadecyl group, and n-hexadecyl group. In addition, examples of the branched hydrocarbon group include 1so-propyl group, iso-butyl group,
1So-pentyl group, l-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, CHi CHCHz
CHz CHz (5-methylhelimethylbentyl group), CH, CI.

(hexyl group), CHi CHCHz CCHz
CH2-1lIs (3,3,5-)limethylhexyl group), CH2CH2 CHs CCHz CM CHz CHt
(3,5,5)suCH3 methylhexyl group), CI3CO3CH.

(limethylbutyl group), CHff-C-CHz-CH-
CHz CHs (1,3,3-)limethylbutyl group), CHsCHzC
LCH(CH3)CLCL-(3-methylhexytrimethylheptyl group), trimethylheptyl group), C1h C)13 CH2CL CHz COCJ CHCH2CH
z-(3,5-dimethyloctyl group), -tetramethylheptyl group), (3,6,9-)limethyldecyl group), CHs
CH, CHz ntamethyl λ xyl group), CH3-CH-CH2CH1CHCH1CH2CH-(
1,4,7-) CH+ CH+
CHx methyloctyl group), CI(.

CHs CI CHzCthCCHz C)l
(1,3,3,6-teCH3CHs CHz tramethylheptyl group), (3,5,6,8-tetramethylnonyl group), CH3C
Hs CHs CH3CCHz CHCHt CCHt CH2
-C)l:I CHs (3,3,5,7-pentamethyloctyl group), (1,
2,4,6,8-pentamethylnonyl group), (4,5,
7,9,11-pentamethylundecyl group) and the like.

The sum of the carbon numbers of R+ and R2 is 8 to 36. When the number is less than 8, the cleaning effect is not sufficient, and when it exceeds 36, the solubility of the resulting compound in fuel decreases. It also produces heat residue.

Considering these characteristics, the carbon chain length of the R+ and lh portions is 3 to 18, and the sum of the carbon numbers of R and R2 is 8 to 18.
36 is preferable, and 10 to 32 are more preferable.

To further explain the compounds represented by formulas (1) to (3), -(BO), - or -(BO) in the amine or amine oxide residue represented by YI''Yz,
+- represents an oxyalkylene or polyoxyalkylene ether structure. In this case, the alkylene group B has 2 carbon atoms.
~4, and the alkylene group used in this case is ethylene, propylene, butylene (1,2-; 2,3-
; 1,3- and 1,4-) groups. Moreover, ■ is O-10.

The method for producing the compounds represented by the above general formulas (1) to (3) is, for example, when R in Yll Yll h is - (0 and E are directly bonded) and E is an alkylene group having 3 carbon atoms. In the case of the following general formulas (8), (9), Gω can be obtained by further repeating cyanoethylation with acrylonitrile and hydrogenation.

The cyanoethylation reaction can be carried out by heating and stirring under a strong alkaline catalyst such as caustic alkali. Also,
Hydrogenation can be obtained by reaction under a hydrogenation catalyst such as Raney nickel.

In addition, to give an example of another synthesis method, as shown in the following,
R2,n+ Il+ 8 has the meaning given above. ) is cyanoethylated with acrylonitrile and then hydrogenated, or this compound (wherein Yll Yz
, Yz is as described above) with an alkoxide reacted with an alkali metal, an alkaline earth metal, or an oxide or hydroxide thereof.

Further, to give a detailed example of the above synthesis method, for example, taking the case of formula (8) of the above synthesis method, the following general formula GO
, Q'lJ are used as they are, or in the form of alkylene oxide adducts of these branched alcohols.

(R5 and R6 are hydrocarbon residues having 3 to 16 carbon atoms and the sum of the carbon numbers of R3 and R6 being 10 to 32, or R?, Re
has 3 to 15 carbon atoms, and the sum of the carbon numbers of R1 and R3 is 8 to
30 hydrocarbon residues. ) Such alcohols are so-called hyperbranched alcohols and can be obtained directly by condensing two molecules of natural or synthetic aliphatic alcohols, for example by reaction to form a gel, or by reaction of acetic anhydride with α-olefins. It can also be obtained by reducing the branched fatty acids obtained in .

Alcohols that can be used as raw materials for the present invention include:
Specifically, for example, 2-butyldodecyl alcohol,
2-Butylhexadecyl alcohol, 2-hexyl octyl alcohol, 2-hexyldecyl alcohol, 2-
Hexyltetradecyl alcohol, 2-hexyl octadecyl alcohol, 2-hebutylnonyl alcohol, 2
-hebutylundecyl alcohol, 2-octyldodecyl alcohol, 2-octylhexadecyl alcohol,
2-nonylundecyl alcohol, 2-nonyltridecyl alcohol, 2-decyldodecyl alcohol, 2-decyltetradecyl alcohol, 2-decyloctadecyl alcohol, 2-undecylpentadecyl alcohol,
2-dodecyltetradecyl alcohol, 2-dodecylhexadecyl alcohol, 2-tridecylhexadecyl alcohol, 2-tetradecylhexadecyl alcohol, 2
-tetradecyl octadecyl alcohol, 2-hexadecyl octadecyl alcohol, 4-hexyldodecyl alcohol, 4-octyltetradecyl alcohol, 4-
Nonylpentadecyl alcohol, 4-decylhexadecyl alcohol, 4-dodecyloctadecyl alcohol,
CHs C83CH3 CH2Cl CHz CI CHCHz CH
z CHCHHz 0HCH3CHCHI CHC
H CHs CHs C1(3 [2-(1°, 2°, 4′-trimethylpentyl) −
5,6,8CHs CHCHCHt CI CH
z CHz C1l CHz 0HCHi
CHCI CHz C) ICI(3CH3CH3 [2-(1°, 3', 4'-trimethylpentyl) -
5,7,8-trimethylnonanol], CL CHz CHz C)l CL CH
CHi CHz CHCHz 0HCHs C
Hz Cut CHCHHz CHCH,CH.

[2-(1',3'-dimethylhexyl) -5,7-
Dimethyldecanol 1, CHx CH3CL CLCHz
CI CHz C1 (CHCHI CI C
Hz CL CHC1l□-0HCH3CHCH2
C)I CHCHI CHC)1. C
H3C1(3CH3[2-(1°, 3', 4', 6"-
tetramethylheptyl)5.7,8.10-tetramethylundecanol], CH3CHCH2CHCHCH2
CL C)I CH20HCHs CHCHCH
z CH CH3C)13 CH3 [2-(1',3',4'-trimethylpentyl)
-5,6,8 trimethylnonanol 1, CHi CH3CH3CH3 CHz CHCHz CHCI CH2CI
CHCH20HCHz CHCHHz CHz C
Hz CHzCH.

[2-(5'-methylhexyl) -3,5,6,8-
Tetramethylnonanol], CHy CB.

CH3CH.

12~(1', 1", 3"-trimethylbutyl) -5
,5,7 trimethyloctanol], C8゜CH3 ct+, C)13 C)13[2-
(1', 1', 3', 5', 5°-pentamethylhexyl)5.5,7,9.9-pentamethyldecanol]C
H3CH3G)+3 CH3CCHz CH CH3CH.

[2-(1',3',3'-)limethylbutyl) -5
,7,7 trimethyloctanol 1, CH.

CH3CH:+-CH-CTo-CHz-C)l-CL-Ct
(2-C)tCH3CHs C)13 [2-(1′,4″,7′-trimethyloctyl)5.
8.11- Trimethyldodecanol 1, CH3CL
CL [2 CH3CCH2CO CH3CH.

(1',3',3"-trimethylbutyl)-trimethyloctatool] 5,5.7 CH3-CH-CJIz-CHz-CC)iz-CHC
H3CH3CHs [2-(1', 3', 3°, 6°-tetramethylheptyl)-5,7,7,10-tetramethylundecanol], C1h-CH-CI(z-CH-CHz-CH -C
Hz-CHCHCH3CH3C[ls CH3C
H3[2-(1'2'',4',6°,8'-heptamethylnonyl)5.6,8,10.12-hebutamethyltridecanol1,[2 (3'-methylbutyl)7 -methyloctatool 1, +2-(1'-methylbutyl)-5-methyloctatool] and the like.

Regarding the chain length of these highly branched alcohols, R5 and R
The total number of carbon atoms in 6 is 10 to 32, preferably 12 to 30. If this is less than IO, the alkyl ether amine obtained therefrom will not have the ability to disperse the sludge, which is undesirable. The sum of the carbon numbers of R7 and R is 8 to 30,
Preferably it is 10-28.

If this is less than 8, the sludge dispersibility also deteriorates. Furthermore, if the sum of the above-mentioned carbon numbers is too large, the resulting alkyl ether amine has poor solubility in fuel oil and cannot be used.

In the case of alkyl ether amines whose raw alcohols are straight-chain alcohols without branches or small branched alcohols such as methyl groups, such as oxo alcohols, they not only have poor solubility in fuel oil, but also have poor cleanliness and thermal decomposition. It was also much less effective in terms of properties aimed at by the present invention, such as properties.

Considering such characteristics, the carbon chain length of the R6 and R6 portions needs to be 3 to I6, and the carbon chain length of the R1 and R11 portions needs to be 3 to I5.

Especially R5, I? , has 6 to 12 carbon atoms, and R
When the sum of the carbon numbers of 5 and R6 is 12 to 22, Rt,
Better results can be obtained when Rs has a carbon number of 5 to If and the sum of the carbon numbers of R7 and RII is II to 21.

If the chain length becomes too large, the solubility in gasoline will decrease as described above, which is not preferable.

The most suitable starting material that satisfies the above-mentioned suitability is a highly branched alcohol obtained by subjecting alcohols of a single composition or a mixture of compositions to a Guerbet reaction.

Performing the above-mentioned cyanoethylation followed by reduction using one or more of the above-mentioned large branched alcohols as they are or their alkylene oxide adducts as starting materials,
If necessary, cyanoethylation and reduction can be performed again to obtain a compound represented by the following general formula (4) or (5).

(In the formula, Rs and Rh have 3 to 16 carbon atoms, and R5 and R
(wherein, R7 and R1 have 3 to 15 carbon atoms, and R, and Rs
a hydrocarbon residue with a total number of carbon atoms of 8 to 30, l is 1 or 2
) R2-R1
As long as 1 has the above-mentioned specific number of carbon atoms, those forming a straight chain,
Further, although any branched carbon chain gives a desirable effect, a straight chain has better cleanliness. In particular, by using as an additive a mixture of a compound in which R5-R8 is a straight-chain hydrocarbon residue and a compound in which R6-R6 is a further branched hydrocarbon residue, the cleanliness can be significantly improved. Effects can be obtained. The most significant effect can be obtained by mixing the former and the latter at a weight ratio of preferably 0.02 to 50, particularly preferably 0.1 to 10.

The raw material alcohols having small branched chain moieties in the large branched chain parts R5 to RB are as described above, but as the small branched chain moiety, those having a methyl branch are particularly preferable.As such large branched alcohols, , propylene dimer to pentamer oxo alcohol, butylene, isobutylene, etc.
It can be easily obtained from a trimeric oxoalcohol or a mixture thereof using the Guerbet method.

Furthermore, in formulas (1) to (3), when R in Y+, Yz, and Y3 is a group selected from -CHIC0NH-, -CHICH(OH)-, or -CHzCo-, for example, the following formula ( After reacting the compound represented by (8), (9) or 00) with chloroacetic acid or epichlorohydrin, reacting with the corresponding amine compound or/and adding an alkylene oxide having 2 to 4 carbon atoms. It can be obtained by

Furthermore, in formulas (1) to (3), when R in YI+ Y□Y is - (0 and E are directly bonded), for example, the following formulas (8) to 00) It can be obtained by halogenating the terminal hydroxyl group with a halide such as phosphorus tribromide and then reacting with a corresponding amine compound or adding an alkylene oxide.

In addition, in formulas (1) to (3), Yl is a group represented by 3 → BO)lI-R → E-N + "Ra,
Alternatively, it can be obtained by reacting a group represented by ↓3ZBO)-1I-R→E-N÷rR4 or a YZ+ compound with an organic peroxide.

However, the synthesis method of the compounds represented by formulas (1) to (3) is as follows:
The method is not limited to the method described above.

The compound of component (B) used in the present invention has the following general formula (I), (II) or (III)H (wherein R3 is an alkyl group having 15 to 100 carbon atoms or (wherein R1 is An alkyl group or alkenyl group having 15 to 100 carbon atoms, A is +NH-(C)12 → NH- or +NH-(
CHt)i-+2r-NH-CO-NH+(CH2-)
yNH+r-1p is an integer of 1 to 3, q is an integer of 0 to 5,
H represents an alkyl group or alkenyl group of 100.

) R4 represents an alkyl group or alkenyl group having 15 to 100 carbon atoms, p represents an integer of 1 to 3, and q represents an integer of 0 to 5. ) R' + NH-(CH!斥→*NH)h...
(I[[) (wherein, RS is an alkyl group or alkenyl group having 15 to 100 carbon atoms, X is H or
00 alkyl group or alkenyl group, p is an integer of 1 to 3, and q is an integer of 0 to 5. ) and has a molecular weight of 700 to 50
00 compound.

This compound has properties as a dispersant in oil and has the ability to disperse engine sludge. It also has high heat resistance and has the effect of compensating for the heat resistance of the (A) 1 minute compound. In order to improve heat resistance, it is necessary to have a molecular weight of 700 or more.If the molecular weight exceeds 5000, the solubility in gasoline will be poor, so it is preferably 3000 or less, and the heat resistance will be too high. In this sense, the molecular weight is preferably 5,000 or less, preferably 3,000 or less, since it does not burn completely in the combustion chamber and remains as a deposit, which has a negative effect on engine performance. In order to have dispersibility in oil, it is necessary to have an alkyl group or alkenyl group having 15 or more carbon atoms and a primary or secondary amino group. As the alkyl group or alkenyl group, for example, a polybutenyl group or a polybutyl group derived using polybutene (butylene polymer) having a molecular weight of 400 or more can be used. Heat resistance can be determined using, for example, a thermobalance (TG 81115) manufactured by Rigaku Denki ■.
The measurement can be carried out under the conditions of 0 d/min, a temperature increase rate of 5°C/lll1n under air flow, and a sample amount of 10 to 14 cm.

It is necessary that the weight loss rate be 70% or less at a temperature of at least 300°C. (A) For compounds with rli, min, 3
The weight loss rate is 90% or more at 00°C.

A typical example of the compound of component (B) is succinimide, which is known as a detergent and is represented by the following structural formula.

(In the formula, q is an integer of O to 5, and Xt represents H or an alkyl group or an alkenyl group (such as a polybutenyl group).) Synthesized by reaction of acid anhydride and polyamine. Generally, polyethylene boria can be used as the agone.

Also preferably used is polybutenylamine represented by the following general formula, which is obtained by chlorinating polybutene and then directly reacting it with a polyamine.

R5° → N H-CHz CHz RN H-χ1 (wherein, R5° is a polybutyl group with a MW of 700 or more, χ3 is H
or a polybutyl group of 700 or more; q represents an integer of 0 to 5; ) Furthermore, benzylamine and its derivatives represented by the following general formula obtained by reacting alkylated phenol, formaldehyde, and polyamine by Mannich reaction can also be used.

H (wherein R1 is an alkyl group or alkenyl group having 15 to 100 carbon atoms,
-CHtCHz)v-NH-Co-NH-(CHzCH
JH) T-q is an integer of 0 to 5, an alkyl group or alkenyl group of 100 or more, and some examples of the compound of component (B) are listed here, but are not limited thereto). When used alone, this component (B) has a cleaning effect on the carburetor, but has a poor cleaning effect on other intake systems. In particular, the cleaning effect of the intake R) reflex is insufficient.

However, the above (A) compound with a Jff of 1 and (B
) When used in combination, the cleaning effect of the inch wool improves, and especially when added in a low amount, an excellent cleaning effect is exhibited.

Furthermore, when the fuel additive of the present invention is used in combination with mineral oil or synthetic oil commonly called G/I/J oil, it exhibits an even more excellent effect of maintaining the cleanliness of the intake system, especially the intake valve, even at a low additive amount.

In particular, the effects of synthetic oils are excellent, especially olefin polymers, such as polyα-olefins and polybutenes, alkylene oxide adducts of alcohols or alkylphenols, and alkylene oxide polymers, especially alkylene oxides such as propylene oxide and butylene oxide. Adducts and their ester or ether compounds are preferred.

More preferred synthetic oils include the following general formula (6) or (
Examples include compounds shown in 7).

Rq-0-<no)-J-R+ or R,-0-(Do)
OCR” ... (6) (In the formula, Rq, R+. are each an alkyl group having 1 to 30 carbon atoms, R゛ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and D is an alkyl group having 3 to 4 carbon atoms. alkylene group, d = an integer of 1 to 50.) The blending ratio of the compound of component (A), the compound of component (B), and mineral oil or synthetic oil is (A) Ifi. of compound/(
B) Component compound/mineral oil or synthetic oil = 1-50/1-3
0150 to 98 (weight ratio) is preferable.

The fuel oil additive of the present invention has a highly branched structure not found in conventional fuel oil additives, and contains an ether bond, an amino group or a derivative thereof in the molecule, and a relatively heat-resistant component (B). By blending these, the cleanliness of high-temperature intake valves is excellent.

The fuel oil additive of the present invention contains 0.1 to 50,
000ppm is blended. The larger the amount added, the better the cleanliness, but at 1 to 20,000 ppm, sufficiently excellent results can be obtained for practical use. The intake system, especially the intake valve, exhibits its excellent ability to maintain cleanliness even at 400 pp+s or less.

The additives of the present invention may be used in combination with other fuel oil additives, such as rust inhibitors, demulsifiers, metal deactivators, and the like. By blending the fuel oil additive of the present invention in this way, a fuel composition with excellent cleanliness can be obtained.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto.

<Synthesis example of compound of component (A)> Synthesis example 1 400 g of 2-octyldodecyl alcohol was placed in a four-hole IE flask, and 0.22 g of caustic potash was added under a nitrogen atmosphere.
Using 2g of acrylonitrile as a catalyst, 83.85g of acrylonitrile was added dropwise over 3 hours while heating and stirring at a temperature of 76 to 80°C, and after the dropwise addition, the mixture was allowed to react at 76 to 80°C for 2 hours, and then the caustic potash that had settled in acetic acid was neutralized. , excess acrylonitrile was removed under reduced pressure to obtain a cyanoethylated product.

300g of this cyanoethylated product was put into 12 autoclaves, and 20kg/c using Raney nickel as a catalyst.
Hydrogenation is carried out by applying a hydrogen pressure of 20.H.
2-octyldodecyloxyprobylamine (A-1
) was obtained.

Synthesis Example 2 1 n-octyl alcohol and 1 n-dodecyl alcohol
: Guerbet reaction was carried out at a molar ratio of 1. From the obtained mixed hyperbranched alcohol, a hyperbranched alkoxypropylamine (abbreviated as A-2) was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 3 Using 2-tetradecyl octadecyl alcohol as the raw alcohol, the formula CrbH3zC was prepared in the same manner as in Synthesis Example 1.
2-tetradecyloctadecyloxyprobylamine represented by H(C+aHze)CBzOCsHbNHz was obtained, and then cyanoethylated in the same manner as in Synthesis Example 1, and then hydrogenated to give the formula % -tetradecyloctadecyloxypropyl Propylene diamine (abbreviated as A-3) was obtained.

Synthesis Example 4 Using 2-hebutylundecanol as the raw alcohol,
A branched alkoxypropylamine (abbreviated as A-4) was obtained in the same manner as in the synthesis example.

Synthesis Example 5 Account Fine Oxocol 140 [Representative Structure Table As an alcohol, in the same manner as in Synthesis Example 1, as a representative structure, a large branched alkoxypropylakone (A-5) represented by or
) was obtained.

Table 1 shows other compound examples of component (A) of the present invention.

<Example of compound of component (8)> Examples of the compound of component (B) * of the present invention used in the examples are shown below.

-1 Rh bipolybutenyl group with molecular weight 900 -2 H R? , a polybutyl group with a molecular weight of 800 -3 R''N)l(JhCLN)It R8: a polybutyl group with a molecular weight of 1000 Example 1 The dispersibility of the additives shown in Table 2 was determined by the following method in order to examine the sludge deposition prevention and removal effects. We conducted a test.

The hexane-insoluble, chloroform-soluble portion of the sludge scraped from the crankcase of an engine after high mileage driving was dissolved in chloroform in a typical base gasoline containing the test additives at a sludge level of 600 ppm.
I added it so that it becomes

Additive concentration: 100 pPII, 200 ppm, 400
pp-, and the amount of sludge was examined 30 minutes after the addition of the sludge solution.

Judgment was made in three stages: ○ when there was no sludge sediment, Δ when there was some sludge, and × when there was a lot of sludge sediment.

Without additives, the sludge is insoluble in gasoline and will precipitate.

The results are shown in Table 2.

R? , a polybutyl group with a molecular weight of 700 (Continued Note) As is clear from the weight ratio Table 2 of the compounding ratio of component (A) and component (B), the product of the present invention has excellent sludge dispersion power.

Example 2 (Actual Vehicle Driving Test) The cleanliness retention ability of the fuel oil additive was evaluated by the following test.

250 p of fuel oil additive to regular gasoline
Driving on a −g road using ps+ added gasoline;
The conditions of the intake system (intake valve, intake boat, carburetor) and combustion chamber before and after the test were evaluated by disassembling the engine and visually observing the degree of deposit adhesion. However, the weight of the intake valve was measured before and after the test to determine the amount of deposit attached. The test car is Toyota Carina 180.
The test was carried out using 0cc (engine type Is).

The test car had its intake system and combustion chamber cleaned before the test.
The deposit was removed and used.

The degree of cleanliness retention before and after the test was determined based on the following criteria. The criteria for evaluating effectiveness was based on the results without the addition of fuel oil additives.

The results are shown in Table 3.

〔Effect of the invention〕

As can be seen from the results of the actual vehicle test in Table 3, the fuel oil additive of the present invention has an excellent ability to maintain the cleanliness of the intake system, especially the intake valve, even when added in a small amount.

Claims (1)

[Scope of Claims] 1. (A) (a) has an alkyl branch having 3 to 18 carbon atoms, and has an alkyl group having 9 to 37 carbon atoms including this branched portion, and (b) An amine or amine oxide having one or more oxyalkylene groups having 2 to 4 carbon atoms, and (B) the following general formula (I), (II) or (III) ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼...(I) (In the formula, R^1 is an alkyl group or alkenyl group with 15 to 100 carbon atoms, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Numerical formulas, chemical formulas , tables, etc. ▼ p is an integer from 1 to 3, q is an integer from 0 to 5, X_1 is H or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R
^2 represents an alkyl group or alkenyl group having 15 to 100 carbon atoms. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, R^3 is an alkyl group or alkenyl group with 15 to 100 carbon atoms, X_2 is H or ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, R^4 is an alkyl group or alkenyl group having 15 to 100 carbon atoms, p is an integer of 1 to 3, and q is an integer of 0 to 5.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (III) (In the formula, R^5 is an alkyl group or alkenyl group having 15 to 100 carbon atoms, X_3 is H or an alkyl group or alkenyl group having 15 to 100 carbon atoms, p is an integer of 1 to 3, and q is 0
Indicates an integer between ~5. ) and a compound having a molecular weight of 700 to 5,000. 2. The compound (A) has the following general formula (1), (2) or (
The fuel oil additive composition according to claim 1, which is a compound represented by 3). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(3) [Formula In the formula, R_1 and R_2 are hydrocarbon residues having 3 to 18 carbon atoms, and the sum of the carbon numbers of R_1 and R_2 is 8 to 3.
It is 6. n is 0 or an integer of 1 to 4. Y_1 is an amine or amine oxide residue represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Y_2,
Y_3 indicates an amine or amine oxide residue represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, B is a carbon number of 2 to 4
alkylene group, m is an integer of 0 to 10, R is -, -CH
_2CONH-, -CH_2CH(OH)-, -CH_
A group selected from 2CO-, E is - or an alkylene group having 1 to 4 carbon atoms, R_3 and R_4 are H or an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group or an aminoalkyl group, and i is 1 or 2. ). 3. The fuel oil additive composition according to claim 1, wherein the compound (A) is a compound represented by the following general formula (4) or (5). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(4) (In the formula, R_5 and R_6 have 3 to 16 carbon atoms and R_5
and R_6, a hydrocarbon residue in which the sum of the carbon numbers is 10 to 32, l
is 1 or 2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(5) (In the formula, R_7 and R_8 have 3 to 15 carbon atoms and R_7
and R_8, the sum of the number of carbon atoms is 8 to 30 hydrocarbon residues, l is 1 or 2) 4, the compound (A) and the compound (B) according to claim 1,
and a mineral oil or synthetic oil. 5. The fuel oil additive composition according to claim 4, wherein the synthetic oil is a compound represented by the following general formula (6) or (7). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (6) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...・(7) (In the formula, R_9 and R_1_0 each have a carbon number of 1 to 30
an alkyl group, R' is hydrogen or an alkyl group having 1 to 20 carbon atoms, D is an alkylene group having 3 to 4 carbon atoms, d = 1 to 50
an integer of 6. The fuel oil additive composition according to claim 4, wherein the synthetic oil is polybutene or its hydrogenated product having a molecular weight of 400 to 2000, or polypropylene or its hydrogenated product.