JPH05117671A - Gasoline additive composition - Google Patents

Abstract

(57) [Summary] [Structure] The composition for gasoline addition of the present invention is selected from the group consisting of monosuccinimide, bissuccinimide, or a mixture of both succinimides.
And a polyoxyalkylene glycol having an average molecular weight of 500 to 5,000 or an ether compound thereof, further having a viscosity of 3
consisting of mm ² / s ~35mm ² / s lubricating oil fraction (100 ° C.). [Effect] It is possible to reduce the amount of deposits adhering to the intake valve and improve the cleanliness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gasoline additive composition, and more particularly to a gasoline additive composition capable of significantly reducing deposits on intake valves of automobile engines.

[0002]

2. Description of the Related Art Conventionally, polyalkenyl succinimide, hydroxypolyether polyamine and the like have been known as cleaning agents for carburetors and engines in automobiles. However, when this kind of succinimide was made to function as a detergent, the cleaning function could not be sufficiently exhibited.

[0003]

SUMMARY OF THE INVENTION The present invention relates to an improvement in this type of gasoline detergent, and in particular to provide a gasoline additive composition capable of reducing deposits in the intake valve of an automobile engine. To do.

[0004]

The composition for adding gasoline of the present invention comprises a monosuccinimide represented by the following general formula 3, a bissuccinimide represented by the following general formula 4, or a mixture thereof. From one selected from mixed succinimides, a polyoxyalkylene glycol having an average molecular weight of 500 to 5000 or an ether compound thereof, and a lubricating oil fraction having a viscosity of 3 mm ² / s to 35 mm ² / s (100 ° C.). It is characterized by

[0005]

[Chemical 3]

(In the formula, R ₁ represents an olefin oligomer group having 30 or more carbon atoms, R ₂ represents a C _{2 to} C ₄ alkylene group, and m represents an integer of 1 to 10.)

[0007]

[Chemical 4]

[0008] (wherein, R _3, R ₃ 'is an olefin oligomer group having at least 30 carbon atoms, R ₄ represents an alkylene group of C ₂ -C _4, n is an integer of 0.) First, The succinimides in the gasoline additive composition of the present invention will be described.

Generally, a polyolefin polymer obtained by polymerizing olefins in the presence of a polymerization catalyst is first reacted with maleic anhydride to give polyalkenyl succinic anhydride, and then polyalkenyl polyamine is added to this polyalkenyl succinic anhydride. Succinimides are prepared by reacting in the presence of a diluent, but monosuccinimides can be prepared by reacting polyalkenyl succinic anhydride and polyalkylene polyamine at a molar ratio of 1: 1 or bissuccinic acid. The imides are obtained by reacting at a molar ratio of 2: 1.

The polyolefin polymer constituting the monosuccinimides has 30 or more carbon atoms, preferably 40 to 400 carbon atoms and an average molecular weight of 500 to 5,000 in consideration of compatibility with gasoline. Good. Examples of the olefin include ethylene, propylene, 1-butene,
Isobutylene, 1-hexene, 2-methylpentene-
It is an α-olefin having 2 to 8 carbon atoms such as 1,1-octene, and is preferably polypropylene or polyisobutylene.

As the polyalkylene polyamine,
It is preferable to use one having a repeating unit number m of 1 to 10 in the above general formula 3, polyethylene polyamine,
Examples thereof include polypropylene polyamine and polybutylene polyamine, with polyethylene polyamine being particularly preferable.

Next, as the polyolefin polymer and polyalkylene polyamine constituting the bissuccinimide, the same ones as those in the above monosuccinimide can be used.

The succinimide mixture contains the above monosuccinimide and bissuccinimide in a weight ratio of 75: 25-.
The ratio is 25:75, preferably 60:40 to 40:60. 1 for the commercially available mono-type succinimide
Since 0 to 25% by weight of bissuccinimide and commercially available bis-type succinimide contain 10 to 25% by weight of monosuccinimide, they are appropriately mixed and prepared.

These succinimides or succinimide mixture are contained in an amount of 10 ppm by weight based on the total amount of gasoline.
It is recommended that the content of ˜5,000 ppm by weight be contained.

Next, as the polyoxyalkylene glycol, the general formula HO-R _1- (OR ₁ ) _n -OH (wherein R ₁ is an alkylene group, preferably ethylene, propylene, butylene, or a mixture thereof) is used. It represents an alkylene group.).

As the ether compound of polyoxyalkylene glycol, monoethers represented by the general formula R ₂ O—R ₁ — (OR ₁ ) _n —OH or general formula R ₂ O—R ₁ — (OR ₁ ) Diethers represented by _n- OR ₃ .

(However, R ₁ is the same as above, and R _1
2 and R _{3 each} represent an aliphatic, cycloaliphatic or aromatic hydrocarbon group. ) In particular, R ₂ and R ₃ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, (t) -butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, benzyl, tolyl, xylyl,
Phenethyl, p-methoxyphenyl, cyclohexyl,
A cyclopentyl group is preferred.

These polyoxyalkylene glycols or their ether compounds have an average molecular weight of 500 to 500.
If the average molecular weight is 500 or less, the effect of preventing deposition of deposits is significantly reduced, and if it exceeds 5000, the fluidity on the intake valve surface is reduced. It is not preferable because it itself becomes a causative substance of the deposit.

The polyoxyalkylene glycol or its ether compound is preferably contained in an amount of 10 ppm by weight to 5,000 ppm by weight based on the total amount of gasoline.

The gasoline additive composition of the present invention, together with succinimide mixture and polyoxyalkylene glycol or its ether compound, the viscosity 3mm ² / s ~35mm ² /
It is characterized by having a lubricating oil fraction of s (100 ° C.) as its constituent component.

The lubricating oil fraction (hereinafter also referred to as carrier oil) has a good compatibility with succinimides and polyoxyalkylene glycol or its ether compound, and the amber after gasoline is evaporated on the surface of the intake valve. Improves the fluidity of acid imides and solubility in base oil,
It has a function of preventing deposition of deposits.

As such carrier oil, 3 mm
A lubricating oil fraction having a viscosity of ² / s to 35 mm ² / s (100 ° C.), for example, a raffinate obtained by subjecting a vacuum distillation distillate to an extraction treatment with a solvent such as phenol, furfural, or N-methylpyrrolidone. Hydrocarbon distillate obtained after solvent dewaxing with a solvent such as propane or methyl ethyl ketone, and then subjecting it to further hydrorefining to improve hue and remove unstable substances (aromatic carbon %, Based on the total number of carbon atoms of 2% to 20%), or a mixture of this hydrocarbon distillate oil and a residual oil which has been subjected to solvent extraction, solvent dewaxing and solvent deoxidation treatment. Further, catalytic dewaxing treatment may be performed instead of solvent dewaxing treatment. Furthermore,
It is also possible to use highly hydrogenated refined oil (percentage of aromatic carbon atoms based on the total carbon number of 2% or less). In terms of composition, these refined mineral oils are paraffinic, naphthenic, etc.
Alternatively, it is a mixed system lubricating oil fraction thereof.

If the viscosity of the carrier oil is less than 3 mm ² / s, it will evaporate together with gasoline and will not function as a carrier oil. If it exceeds 35 mm ² / s, the fluidity will decrease and the carrier oil itself will be the causative agent of deposits. It is not preferable because it becomes.

The carrier oil may be mixed in an amount of 0.5 to 5 parts by weight with respect to 1 part by weight of an additive composed of succinimides and polyoxyalkylene glycol or an ether compound thereof.

The gasoline additive composition of the present invention may be diluted with an organic solvent before use or storage. Organic compounds that are inert as such solvents, such as kerosene, benzene, toluene, xylene, ethylbenzene, propylbenzene, trimethylbenzene, chlorobenzene, methoxybenzene, ethoxybenzene, pentane, hexane, heptane, octane, nonane, decane, undecane. , Dodecane, cyclohexane, cyclopentane, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl ether, propyl ether, isopropyl ether, butyl ether, isoamyl ether, isobutyl ether, methyl n-propyl ether, methyl isobutyl ether, methyl Amyl ether and ethyl n-butyl ether are preferred, and toluene, xylene, ethylbenzene and trimethylbenzene are particularly preferred, alone or It may be used in combination with these.

The gasoline to which the composition of the present invention is added is
It is a normal automobile fuel having a gasoline boiling range obtained from straight-distilled naphtha, polymerized gasoline, natural gasoline, or a feed oil obtained by catalytic cracking or thermal cracking or catalytic reforming.

In addition to the composition of the present invention, octane number improvers such as methyl tert-butyl ether (MTBE), antistatic agents, corrosion inhibitors, antioxidants, antifreezing agents, dyes, etc. It may be added.

[0028]

The composition for gasoline addition of the present invention has a lubricating oil fraction having a succinic effect in addition to the cleaning action of succinimides and the action of preventing deposit adhesion by polyoxyalkylene glycol or its ether compound. It functions as a carrier oil for acid imides, polyoxyalkylene glycols or its ether compounds, and can enhance the fluidity and solubility of additives, so it has excellent thermal stability as a gasoline additive composition and can be dispersed in gasoline. The effect can be made excellent, and in particular, it is possible to effectively prevent the deposition of deposits on the metal surface of the intake valve and the like in an automobile engine.

Hereinafter, the composition for adding gasoline of the present invention will be described with reference to Examples.

[0030]

【Example】

(1) Properties of gasoline used Density 0.752g / cm ² (15 ℃), Reid vapor pressure 0.750Kgf / cm ² (37.8 ℃), aromatic content 40.2%, olefin content 19.6%, 10% Distillation temperature 46.5 ° C., 50% Distillation temperature 99.0 ° C., 90% Distillation temperature 147.0 ° C. (2) Commercially available mono-type succinimide (containing 20 wt% of bis form) Substituted with polyisobutenyl group Polyethylene polyamine having m = 4 and an average molecular weight of about 1500 (G
(Measured by PC method) (3) Commercially available bis-type succinimide (containing 20% by weight of mono-form) Polyisobutenyl group substituted, n = 3 in polyethylene polyamine, average molecular weight of about 2500 (G
(Measured by PC method) (4) Lubricating oil fraction Lubricating oil having a viscosity of 4.7 mm ² / s (100 ° C.) (150 neutral oil, ndM analysis result, percentage of paraffin carbon number to total carbon number 70) 0.0%, percentage of naphthene carbon number to total carbon number 25.0%, percentage of aromatic carbon number to total carbon number 5.0%) Based on the total amount of gasoline having the above properties, the mono-type succinimide , Bis-type succinimide, or a mixture of both {and mono-type / bis-type ratio (weight ratio)}, polyoxypropylene glycol (average molecular weight 1000) or polyoxypropylene glycol monobutyl ether (average molecular weight 1000), Lubricating oil fraction (carrier oil) was added in the ratio shown in Table 1 below (the addition amount is weight p
pm), sample oils 1 to 5 of the present invention, and comparative oils 1, 2, 3,
4 was prepared. The preparation conditions were an oil temperature of 40 to 60 ° C. and a stirring time of about 30 minutes.

[0031]

[Table 1]

This sample oil, comparative oil and multi-grade oil (SAE engine oil viscosity number 10W3 as engine oil
0) was used to carry out a deposit accumulation test on the intake valve by an actual machine.

This test is based on the Toyota IG connected to a dynamometer.
-Using an FE type engine (in-line 6-cylinder 4-valve system), after operating for 100 hours under predetermined conditions, disassembling the engine and taking out the intake valve, intake by the visual judgment based on the CRC method and the weight method of direct weighing. The amount of deposits adhering to the valve was evaluated.

The visual judgment was performed according to the CRC method evaluation scale from the maximum adhesion amount evaluation point 1 to the evaluation point 10 with no deposit. The intake valve was weighed at room temperature within 1 hour after the intake valve was taken out of the engine. The weight of the deposited deposit was determined by subtracting the weight of the clean intake valve measured in advance before the test from the weight of the intake valve after the test. In addition, the number of samples (intake valve) is n in both CRC method evaluation and gravimetric method.
= 12.

The results are shown in Table 2 below.

[0036]

[Table 2]

From these results, gasoline containing succinimides, polyoxyalkylene glycols or ether compounds thereof and lubricating oil fractions was found to be gasoline containing no succinimides and polyoxyalkylene glycols or ether compounds thereof. It can be seen that the amount of deposited deposits is reduced and the cleanliness is improved, as compared with gasoline without addition of gasoline.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10M 101: 02 7419-4H 133: 56 145: 36) C10N 20:02 30:04 40:25 (72) Invention Person Kiyomi Adachi 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute

Claims (1)

[Claims] 1. One selected from a monosuccinimide represented by the following general formula 1, a bissuccinimide represented by the following general formula 2, or a mixed succinimide in which both are mixed, and an average. A gasoline additive composition comprising a polyoxyalkylene glycol having a molecular weight of 500 to 5000 or an ether compound thereof, and a lubricating oil fraction having a viscosity of 3 mm ² / s to 35 mm ² / s (100 ° C.). [Chemical 1] (In the formula, R ₁ represents an olefin oligomer group having 30 or more carbon atoms, R ₂ represents a C _{2 to} C ₄ alkylene group, and m is 1 to
Indicates an integer of 10. ) [Chemical 2] (In the formula, R ₃ and R ₃ ′ represent an olefin oligomer group having 30 or more carbon atoms, R ₄ represents a C _{2 to} C ₄ alkylene group,
n shows the integer of 0-10. )