JPH0488089A - Additive composition for gasoline - Google Patents

Abstract

PURPOSE:To provide the subject composition capable of remarkably reducing deposits at the intake valves of engines for automobiles by compounding a benzylamine derivative having a specific mol.wt. and an ester as main components. CONSTITUTION:The objective composition comprises (A) a benzylamine derivative represented by the formula (R is an alkyl derived from a polyolefin polymer having a mol.wt. of 500-4500; R' is alkylene; n is 1-10) and (B) an ester [e.g. isodecyl butanoate, di(2-ethylhexyl) adipate or neopentyl glycol di(heptanoate)] as main components and preferably further (C) a lubricant fraction having a viscosity of 3-35mm<2>/S (100 deg.C).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a gasoline additive composition, and more particularly to a gasoline additive composition that can significantly reduce deposits in the intake valves of automobile engines.

[Conventional technology]

Conventionally, polyalkenylsuccinimide and hydroxypolyether polyamine have been known as cleaning agents for carburetors and engines in automobiles, and polyalkenylsuccinimide and oxy compounds are dispersed in organic solvents such as xylene as gasoline additive compositions. Alternatively, dissolved ones are also known.

[Problem to be solved by the invention]

The present invention relates to improvements in this type of gasoline additive composition, and in particular, it is an object of the present invention to provide a gasoline additive composition that significantly reduces deposits in intake valves.

[Means to solve the problem]

The gasoline additive composition of the present invention mainly contains a benzylamine derivative having a molecular weight of 500 to 5,000 and an ester represented by the following general formula.

General formula (wherein R is an alkyl group derived from a polyolefin polymer with a molecular weight of 500 to 4,500, R' is an alkylene group,
n represents an integer of 1 to 10. ) Furthermore, the gasoline additive composition of the present invention is characterized in that a lubricating oil fraction having a viscosity of 3 mm2/s to 35 mm2/s (100°C) is further added to the above gasoline additive composition. do.

A method for producing the benzylamine derivative represented by the above general formula is, for example, by alkylating 2-hydroxybenzylamine with a polyolefin polymer in the presence of an acid catalyst and then reacting it with a polyalkylene polyamine.

Examples of the monomer components of the polyolefin polymer include ethylene, propylene, 1-butene, isobutylene,
It can be an α-olefin having 2 to 8 carbon atoms such as 1-hexene, 2-methylpentene-1,1-octene,
Preferred are propylene and isobutylene. The molecular weight of the polyolefin polymer is preferably 500 to 4,500 in consideration of compatibility with gasoline.

Further, as the polyalkylene polyamine polymer, it is preferable to use one having a repeating unit number n of 1 to 10 in the general formula, and examples thereof include polyethylene polyamine, polypropylene polyamine, polybutylene polyamine, etc., and polyethylene polyamine is particularly preferred.

The molecular weight of the benzylamine derivative thus produced is 500 to 5,000. Preferably 1000-300
If the molecular weight is less than 500, the effect of preventing deposits from adhering will be significantly reduced;
If it exceeds 0, the fluidity on the surface of the intake valve will decrease and it will become a cause of deposits, which is not preferable.

Benzylamine derivative is 10p based on the total amount of gasoline.
It is preferable to add it in an amount of pm to 5000 ppm.

Next, as esters, monoesters, diesters,
Examples include polyol esters.

The monoester in the present invention is obtained by an esterification reaction between an alcohol having 4 or more carbon atoms and an organic acid having 4 or more carbon atoms.

Examples of alcohols having 4 or more carbon atoms include n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptatool, isoheptatool, octatool, 2-ethylhexanol, n -nonyl alcohol, isononyl alcohol, n-decylalconobeiisodecyl alcohol, undecanol, lauryl alcohol, stearyl alcohol, etc., preferably 2-ethylhexanol, isononyl alcohol, isodecyl alcohol.

Examples of organic acids include n-butanoic acid, isobutanoic acid,
η-pentanoic acid, isopentanoic acid, n-hexanoic acid, 2-
Ethyl butanoic acid, cyclohexanoic acid, n-hebutanoic acid,
Isohebanoic acid, methylcyclohexanoic acid, n-octanoic acid, dimethylhexanoic acid, 2-ethyl hexanic acid, 2
．． 4. 4 trimethylpentanoic acid, isooctanoic acid,
3,55-trimethylhexanoic acid, n-nonanoic acid, isononanoic acid, isodecanoic acid, isoundecanoic acid, 2-butyloctanoic acid, tridecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid, preferably hebutanoic acid, n -Octanoic acid, 2-ethylhexanoic acid.

The synthesis of esters from alcohols and organic acids can be carried out by conventional methods, such as dehydration condensation under acidic catalysts.

Preferred monoesters include isodecyl butanoate, isodecyl hebutanoate, isodecyl octanoate, 2-ethylhexylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyldecanoate, isononyl Heptanoate, isononyl alcohol, isononyl undecanoate, and the like.

Furthermore, the diester that can be used in the present invention is one obtained by an esterification reaction between an alcohol and a dicarboxylic acid.

Examples of alcohol include methanol, ethanol,
n-propatool, impropatool, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptatool, isoheptatool, octatool, 2-ethylhexanol, n -nonyl alcohol, isononyl alcohol, n-decyl alcohol, isodecyl alcohol, undecanol, lauryl alcohol, stearyl alcohol, etc., preferably 2-ethylhexanol, isononyl alcohol, isodecyl alcohol.

Examples of dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, damaric acid, corkic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid,
Tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanonic acid, octadecanoic acid, nonadecanonic acid, icosaniic acid, phthalic acid, terephthalic acid, etc., and preferably adipic acid, azelaic acid, sebacic acid, and phthalic acid.

The diesterification reaction between an alcohol and a dicarboxylic acid can be carried out by a conventional method, for example, a method of dehydration condensation under an acidic catalyst.

Preferred diesters include di(2-ethylhexyl) adipate, dioctyl adipate, diisononyl adipate, diisodecyl adipate, di(2-ethylhexyl) azelate, diisononyl azelate, dioctyl sebacate, diisodecyl sebacate, di(2-ethylhexyl) phthalate, and the like. It is.

In addition, the polyol ester used in the present invention includes:
It is produced by synthesis of a polyol having 5 to 9 carbon atoms and an organic acid having 4 to 18 carbon atoms.

Examples of polyols having 5 to 9 carbon atoms include 22-dimethylpropane-1,3-diol (i.e., neopentyl glycol), 2-ethyl-2-butyl-propane-1
, 3-diol, 2.2 diethylpropane-1,3-diol, 2,2 dibutylpropane-1,3-diol,
2-methyl-2-propylpropane-1,3-diol, 2-ethyl-2-butylpropane-1,3-diol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, preferably neopentyl glycol , 2-methyl-2-propylpropane-1,3-dionobetrimethylolpropane, and pentaerythritol, and particularly preferred are neopentyl glycol, trimethylolpropane, and pentaerythritol.

Further, organic acids include, for example, n-butanoic acid, isobutanoic acid, n-
Pentanoic acid, isopentanoic acid, n-hexanoic acid, 2-ethylbutanoic acid, cyclohexanoic acid, n-hebutanoic acid, isohebanoic acid, methylcyclohexanoic acid, n-octanoic acid, dimethylhexanoic acid, 2-ethylhexanoic acid, 2 ，
4.4-) Limethylpentanoic acid, isooctanoic acid, 3,
5.5 trimethylhexanoic acid, n-nonanoic acid, isononanoic acid, isodecanoic acid, isoundecanoic acid, 2-butyloctanoic acid, tridecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid, preferably hebutanoic acid,
These are n-octanoic acid and 2-ethylhexanoic acid.

Synthesis of a polyol ester from an organic acid and a polyol can be carried out by a conventional method, for example, a method of dehydration condensation under an acidic catalyst.

Hereinafter, neohentyl will be abbreviated as NPC, trimethylolpropane will be abbreviated as TMP, and pentaerythritol will be abbreviated as PE as preferred polyol esters. ), NPC-di(heptanoate), NPC-di(2-ethylbutanoic acid)), NPC-di(cyclohexanony)),
NPC-G (heptany), NPC-G (isoheptanoate), NPG-G (octylate),
NPG-G (2-ethylhexanoate), NPG-G
G (isooctanoate), NPC G (isononylate), NPC G (isodecanoate), NP
C.G (mixed (hexanoate, heptanoate))
, NPC・G (mixed (hexanoate octanoate')), NPC・G (mixed (hexanoate,
nonylate)), NPC-G (mixed (heptanoate, octanoate)), NPC-G (mixed (heptanoate, nonylate)), NPC-G (mixed (heptanoate, isooctanoy))), NPC-G (mixed (heptanoate, isononylate)) )),NP
C・G (mixed (isooctanoate, isononylate)), NPC・G (mixed (butanoate, tridecanoate))), NPC・G (mixed (butanoate, tridecanoate))
Tetrazocaate)), NPG・G [mixed (butanoate, hexadecanoate))), NPC・G (mixed (butanoate))).

octadecanoate)), NPC・G (mixture (hexanoate, isooctanoate, isononylate))
, NPC・G (mixed (hexanoate, isooctanoate, isodecanoate)), NPC・G (mixed (heptanoate, isooctanoate, isononylate)), NPC・G (mixed (heptanoate, isooctanoate, isodecanoate)) ), NPC・G (mixed (octanoate, isononylate, isodecanoate)), TMP・Tree (pentanoate),
TMP-tri(hexanoate), TMP-1-di(heptanoate), TMP-tri(octanoate), TMP-tri(nonylate), TMP-tri(isopentanoate), TMP-tri(2-ethylbutyrate) , TMPi-G (isopentanoate)
, TMP tri(isooctanoate) , TMP
・Tory (2-ethylhexanoate), TMP・Tory (isononylate), TMP・Tory (isodecanoate), TMP・Tory [mixture (butyrate, octadecanoate)], TMP・Tory [mixture (hexanoate, hexadecanoate)] )) , TMP Tory [Mixed (heptanoate, tridecanoate))), T
MP Tree [Mixed (octanoate, decanoate)
], TMP tri [mixture (octanoate, nonylate)], TMP tri [mix (butyrate, heptanoate, octadecanoate)], TMP tri [mix (pentanoate, heptanoate, tridecanoate)], TMP tri [mixture] (hexanoate, heptanoate, octanoate)], PE/tetra (
pentanoate), PE tetra(hexanoate),
PE・tetra (isopentanony)), PE・tetra (2-ethylbutyrate), PE・tetra (inheptanoate), PE・tetra (isooctanoate),
PE・tetra (2-ethylhexanony)), PE・tetra (isononylate), PE・tetra (oleate)
, and esters of PE and mixtures of straight or branched carboxylic acids having 4 to 8 carbon atoms.

Also, neopentyl polyols other than NPG, TMP and PE, i.e. 2-methyl-2-propylpropane-1,3
Examples include esters of -diol, 2,2-diethylpropanediol, trimethylolethane and hydrimethylolhexane, and the above-mentioned organic acids alone or in combination.

These esters are contained at 10 ppm based on the total amount of gasoline.
It is preferable to add it to contain up to 5000 ppm.

In the gasoline additive composition of the present invention, the benzylamine derivative exhibits a deposit-preventing effect by adhering to the intake valve surface together with the ester.

In addition, the ester has the function of preventing the deposition of deposits on the intake valve surface, and also has the function of increasing the fluidity of the benzylamine derivative after gasoline evaporates on the intake valve surface, increasing its solubility in gasoline, and is a so-called carrier oil. It is presumed that it functions as

In addition, a lubricating oil fraction is added as a carrier oil if necessary, but the lubricating oil fraction has good compatibility with benzylamine derivatives and esters, and the benzylamine derivative after gasoline evaporates on the intake valve surface. It has the function of increasing fluidity and solubility in gasoline and preventing deposits from being deposited.

Such a lubricating oil fraction is 3 mm2/s to 35 m
There are lubricating oil fractions with a viscosity of m2/s (100°C), for example, raffinate obtained by extracting vacuum thin section distillate oil with a solvent such as phenol, furfural, or N-methylpyrrolidone, which is extracted with propane, methyl ethyl ketone, etc. Hydrocarbon distillate oil obtained after solvent dewaxing treatment with a solvent and further hydrorefining as necessary to improve hue and remove unstable substances, or this hydrocarbon distillate oil and residual oils subjected to solvent extraction, solvent dewaxing and solvent deasphalting treatments can be used. Further, catalytic dewaxing treatment may be performed instead of solvent dewaxing treatment.

These refined mineral oils are lubricating oil fractions that are either paraffinic, naphthenic, etc., singly, or a mixture of these.

If the viscosity of the lubricating oil fraction is less than 3 mm2/s, it will evaporate along with gasoline and will no longer function as a carrier oil, and if it exceeds 35 mm2/s, the fluidity will decrease and the lubricating oil fraction itself will accumulate. It is not desirable because it becomes a causative agent of things.

The lubricating oil fraction is preferably used in an amount of 0.1 to 5 parts by weight based on 1 part by weight of the total amount of the benzylamine derivative and ester.

The gasoline to which the composition of the present invention is added includes straight-run naphtha,
It is a common automotive fuel with a gasoline boiling range obtained from polymerized gasoline, natural gasoline, or catalytically cracked or thermally cracked or catalytically reformed feedstocks.

In addition to the composition of the present invention, for example, methyl tart
- octane improvers such as butyl ether (MTBE),
Antistatic agents, corrosion inhibitors, antioxidants, anti-icing agents, dyes, etc. may be added.

[Action and effect of invention]

The gasoline additive composition of the present invention contains a benzylamine derivative, an ester, and if necessary, a viscosity of 3 mm2/s.
~35mm2/s (100°C) as the main component, it has excellent thermal stability, and in addition to the deposit prevention effect due to benzylamine derivatives and esters, esters or lubricating oil fractions are added. It functions as a carrier oil for agents, has an excellent dispersion effect in gasoline, and can effectively prevent deposits from adhering to metal surfaces such as intake valves.

The gasoline additive composition of the present invention will be explained below with reference to Examples.

[Example 1] Density 0.752 g/cm2 (15°C), Reid vapor pressure 0
．． 750 Kgf/cm2 (37.8℃), aromatic content 402%, olefin content 1966%, 10% distillation temperature 4
6.5℃, 50% distillation temperature 99.0℃, 90% distillation temperature 147.0℃ gasoline with distillation properties; (In the formula, R is a polyisobutenyl group with a weight average molecular weight of 12,000, and n is about 8.)
.

Sample oil 1 was prepared by adding it to gasoline so as to contain it.

Using this sample oil 1 and a multigrade oil (SAE engine oil viscosity number 10W30) as an engine oil, a deposit accumulation test on an intake valve was conducted using an actual machine.

For this test, a Toyota IGFE engine (inline 6 cylinder 4 valve system) connected to a dynamometer was used, and after operating for 100 hours under specified conditions, the engine was disassembled, the intake valves were taken out, and deposits were removed. The condition was visually evaluated based on the evaluation criteria of the CRC method using a 10-point scale ranging from score 1 for the maximum amount of deposits to score 10 for no deposits. In addition, the weight of the deposit was determined by direct measurement. The number of samples (intake valves) was 12.

The results are shown in the table below.

[Example 2] In the gasoline additive composition in Example 1, the viscosity was further increased to 4. 7mm2/s (100℃) lubricating oil (
150 neutral oil) to 100% of the total amount of gasoline.
Sample oil 2 was prepared by adding the sample oil so as to contain ppm by weight.

Using this sample oil 2, the same test as in Example 1 was conducted, and the results are also shown in the table.

[Example 3] In place of the ester in Example 1, the same amount of diisononyl adipate was added to prepare sample oil 3.

Using this sample oil 3, the same test as in Example 1 was conducted, and the results are also shown in the table.

[Comparative Example 1] Comparative oil 1 was prepared using only gasoline without adding any additives in Example 1, and the same tests as in Example 1 were conducted. The results are also shown in the table.

(Margin below) Applicant: Tomoen Co., Ltd.

Claims (1)

[Claims] (1) A gasoline additive composition containing as main components a benzylamine derivative having a molecular weight of 500 to 5,000 and an ester represented by the following general formula. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is an alkyl group derived from a polyolefin polymer with a molecular weight of 500 to 4,500, R' is an alkylene group,
n represents an integer of 1 to 10. )(2) The gasoline additive composition according to claim 1 further has a viscosity of 3 mm^2/s or more.
A gasoline additive composition containing a lubricating oil fraction of 35 mm^2/s (100°C).