JPH03247694A - Gasoline additive - Google Patents

Abstract

PURPOSE:To provide a gasoline additive having excellent cleanability and good thermal decomposability and readily synthesized by compounding the reaction product of a compound such as an aliphatic alcohol or an aliphatic amine with a polyisocyanate. CONSTITUTION:The objective gasoline additive contains the reaction product of (A) a compound selected from (i) the 2-6C alkylene oxide adduct of an aliphatic alcohol, alkylphenol, carboxylic acid or amine and (ii) an aliphatic amine or an alicyclic or heterocyclic amine with (B) a polyisocyanate having plural isocyanate groups usually at room temperature 150 deg.C (preferably 40-120 deg.C).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a fuel oil additive, particularly a gasoline additive, and more particularly, to a gasoline additive that is effective in cleaning the fuel intake system and combustion chamber. Regarding.

[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 the intake valves and intake boats cause a reduction in engine output, poor 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 of intake pulp have recently become a major problem. Particularly recently, in Japan, the rate of installation of electronically controlled fuel injection devices in passenger cars has been increasing. Electronically controlled fuel injection devices precisely control the gasoline mixture and are effective not only in improving engine performance but also in fuel efficiency and exhaust emissions. However, when deposits adhere to the intake pulp, gasoline injected from the injection device hits the deposits, disrupting control of the gasoline mixture, and as a result, drivability is adversely affected.

Various fuel additives have been proposed to solve these problems. For example, polyetheramines are disclosed in Japanese Patent Publications No. 48556/1980, 39278/1982, 25489/1989, 33016/1980, and the like. These polyetheramines cannot be said to have a sufficient cleaning effect on intake valves.

In view of the above-mentioned circumstances, an object of the present invention is to provide a gasoline additive that has excellent cleanliness, good thermal decomposition properties, and is easy to synthesize.

[Means to solve the problem]

In order to solve the problems 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) an alkylene oxide adduct having 2 to 6 carbon atoms of an aliphatic alcohol, an alkylphenol, a carboxylic acid or an amine; and b) an aliphatic amine or a group of alicyclic or heterocyclic amines. The present invention provides a gasoline additive characterized by containing a reaction product of one or more compounds selected from the above and c) a polyisocyanate having two or more isocyanate groups.

As the compound a) in the present invention, a compound represented by the following general formula (1) is particularly preferable.

R-X-(80), -H... (1) [Here, R is an aliphatic hydrocarbon residue having 6 to 36 carbon atoms or an alkylphenyl group, or one nitrogen atom or oxygen atom, or Indicates an aliphatic hydrocarbon residue having two or more, X
is 10C0-0--NR", or -N((80)m1H
)-, A represents an alkylene group having 2 to 6 carbon atoms,
m and n are integers of 1 to 50, and R represents a hydrocarbon residue having 1 to 22 carbon atoms. ] In addition, as the amine in b) above, in particular, the nitrogen atom is 1 to 1.
Aliphatic amines or cycloaliphatic or heterocyclic amines having 3 are preferred.

The aliphatic alcohol used as the raw material of the present invention is preferably an alcohol having 6 to 30 carbon atoms, such as hexyl alcohol, octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, eicosyl alcohol, Natural alcohols such as behenyl alcohol, linear alcohols having 6 to 30 carbon atoms obtained by the Ziegler method, branched alcohols having 7 to 24 carbon atoms obtained by oxo reaction, and 16, 18, 20, etc. carbon atoms obtained by Guerbet reaction. 24
m alcohols having a branched alkyl group or an unsaturated hydrocarbon group having 6 to 30 carbon atoms, such as Guerbet alcohol and oleyl alcohol, can be mentioned.

The alkylphenol preferably has 4 to 3 carbon atoms.
The number of alkyl groups is preferably 1 or 2. For example, butylphenol, amylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, cumylphenol, carbon number Examples include alkylphenols having 18 to 24 carbon atoms or 20 to 24 carbon atoms.

Alternatively, an alkylphenol obtained by reacting an α-olefin having 6 to 30 carbon atoms with phenol can also be used.

As the carboxylic acid, m-carboxylic acids having 6 to 30 carbon atoms are preferred. Examples of such -valent carboxylic acids include:
For example, monovalent carboxylic acids having a linear alkyl group having 11 to 30 carbon atoms such as myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid; isostearic acid;
Branched alkyl groups having 6 to 30 carbon atoms such as 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, isodecanoic acid, isotridecanoic acid, oleic acid, erucic acid, linoleic acid, etc. m carboxylic acids having unsaturated hydrocarbon groups are preferred.

The amine serving as the raw material for component a) has 1 to 1 nitrogen atom.
An amine having three atoms (which may contain an oxygen atom) is preferable, and it is particularly preferable to have a primary or secondary amino group. Such amines include, for example, amines with a carbon number of 1
-22 alkyl monoamines and dialkyl amines, 2
- Monoamines such as ethylhexyloxypropylamine, 3-ethoxypropylamine, 3-methoxypropylamine; diamines such as ethylenediamine, 3-diethylaminopropylamine, dibutylaminopropylamine, monomethylaminopropylamine, dimethylaminopropylamine; diethylenetriamine and triamines such as methyliminobispropylamine.

Heterocyclic organic amines such as piperazine, methylbiperazine, hydroxyethylpiperazine, benzotriazole, methylbenzotriazole, and morpholine can also be used.

The alkylene oxide of the alkylene oxide adduct of the aliphatic alcohol, alkylphenol, carboxylic acid or amine mentioned above is an alkylene oxide having 2 to 6 carbon atoms, preferably propylene oxide,
Butylene oxides, particularly preferred are butylene oxides (1,2-; 2,3-; 1.3- and 1.4-). Furthermore, the number of added moles is 10
A range of 50 moles is preferred.

The alkylene oxide adduct a) can be produced by various methods. For example, using an appropriate solvent if necessary, alkylene oxide having 2 to 6 carbon atoms (ethylene oxide, propylene oxide, butylene oxide, etc.) is converted into a liquid or gaseous state while heating alcohol in the presence of a catalyst such as caustic alkali. Add and react. Random addition polymerization in which two or more types of alkylene oxides are mixed and reacted together, or block addition polymerization in which one type of alkylene oxide is sequentially added first may be performed.

As the amine b) used in the present invention, the amine serving as a raw material for component a) described above can be used, but it is necessary to be an aliphatic amine, or an alicyclic or heterocyclic amine. Particularly preferred are secondary amines and tertiary amines.

These amines can be used in combination with the alkylene oxide adduct in a) and reacted with the polyisocyanate in C) to obtain the gasoline additive of the present invention.

The polyisocyanate C) used in the present invention is a polyisocyanate having two or more isocyanate groups (NCO groups) in the molecule. Such a polyisocyanate has 6 to 2 carbon atoms (excluding the carbon in the NGO group).
Aromatic polyisocyanates having 0 carbon atoms, aliphatic polyisocyanates having 2 to 18 carbon atoms, and araliphatic polyisocyanates having 8 to 15 carbon atoms are preferred. Specifically, for example, TD
I (tolylene diisocyanate), 2.4-TD
Depending on the mixing ratio of I and 2.6-TDI, TDI-100
(2,4-TD1100%), TDI-80 (2,4
-TDI/2,6-TDI=80/20) mTDI-6
5 (2,4-TDI/2,6-TDI = 65/35)
are common commercially available products, and 2,4-TDI and 2.
Various mixing ratios of 6-TDI are also available. Others, pure MDI (diphenylmethane diisocyanate)
Crude MDI (crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; mixture of diaminodiphenylmethane and a small amount (e.g. 5 to 20% by weight) of trifunctional or higher functional polyamine] phosgenide) NDI (1,5-naphthalene diisocyanate) mTODI (torizine diisocyanate), HDI (hexamethylene diisocyanate),
IPDI (isophorone diisocyanate) mp-phenylene diisocyanate, transcyclohexane-1
, 4-diisocyanate, XDI (xylylene diisocyanate), H6XDI (hydrogenated XDI) mH12MD
I (hydrogenated MDI) mLDI (lysine isocyanate)
, TMXDI (tetramethylxylene diisocyanate) m lysine ester triisocyanate, 1,6.11
-undecane triisocyanate, 1,8-diisocyanate 4-isocyanate methyloctane, 1,3.6
Hexamethylene triisocyanate, bicyclohebutane triisocyanate, TMDI (trimethylhexamethylene diisocyanate), etc. can be used. Particularly preferred are aliphatic isocyanates and alicyclic isocyanates.

The gasoline additive of the present invention comprises the components a) and b described above.
) one or more compounds selected from the components;
These are urethane and urea compounds obtained by reacting with component C). The reaction is preferably carried out in such a way that the ratio of the alkylene oxide adduct of (a) or/and the amine of b) to the polyisocyanate of C) is substantially (-0H+NHz)/NCO=1. OH group of alkylene oxide adduct of aliphatic alcohol, alkylphenol or carboxylic acid and NCO of polyisocyanate
The ratio between the alkylene oxide adduct of the amine or the OH group or NH2 group of the amine and the NGO group of the polyisocyanate is OH or NHz/NC0=0.5 to 1. More preferably, the ratio of the OH group of the alkylene oxide adduct of aliphatic alcohol, alkylphenol or carboxylic acid to the NCO group of the polyisocyanate is O~0.5.
OH/NCO=0.5 to 0.9, and the ratio of the alkylene oxide adduct of the amine or the OH group or NHz group of the amine to the NCO group of the polyisocyanate is OH or NH2/NC0=0.1 to So that it is 0.5,
It can be obtained by reacting usually at room temperature to 150°C, preferably 40 to 120°C.

A catalyst is usually not required for the reaction, but if the reaction rate is slow, an appropriate catalyst can be used. Examples of the catalyst include amines (triethylamine, triethylenediamine, N-methylmorpholine, etc.), organometallic compounds (dibutyltin dilaurate, stannous octoate, etc.), and the like.

The reaction proceeds satisfactorily without the use of a solvent, but if the reactant has a high viscosity, an appropriate solvent that does not react with components a) to C), which are the raw materials, may be used. Suitable solvents include aliphatic hydrocarbons such as paraffin, olefin, and cycloparaffin, aromatic hydrocarbons such as toluene and xylene, and petroleum solvents such as kerosene, light oil, and solvent naphtha.

When the gasoline additive of the present invention is used in combination with mineral oil or synthetic oil, which is generally called a carrier oil, it exhibits excellent deposit removal effects and cleanliness retention effects. In particular, the effects of synthetic oils are excellent, especially olefin polymers,
For example, poly-α-olefins, polybutenes, etc., alkylene oxide adducts of alcohols or alkylphenols, alkylene oxide polymers, particularly alkylene oxide adducts such as propylene oxide and butylene oxide, and their esters or ether compounds are excellent. The blending ratio is 1 part by weight of the urethane or urea compound of the present invention to 0.00 parts by weight of mineral oil or synthetic oil.
05 to 20 parts by weight is preferred.

The gasoline additive of the present invention contains 0.1 to 50%
．． OOOppm is blended. The larger the blending amount, the better the cleanliness. Practically sufficient results can be obtained at OOOppm. The additive of the present invention may be used in combination with other gasoline additives such as rust inhibitors, demulsifiers, antioxidants, metal deactivators, etc. By blending the gasoline 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 1 Nonylphenol (BO) z. [20 moles of 1,2-butylene oxide adduct of nonylphenol] was added to 5I! , into a flask and heated under nitrogen atmosphere for 10 minutes.
While heating and stirring at 0'C, 1 mol of HDl was added dropwise, and after the dropwise addition, the mixture was reacted at 100C for 2 hours to obtain an additive.

Synthesis Example 2 1.5 moles of nonylphenol (BO) zs (25 moles of 1,2-butylene oxide adduct of nonylphenol) and 1 mole of HDI were mixed in the same manner as in Synthesis Example 1 to 100%
After reacting for 611 hours, 2-methylbiperazine 0.
5 mol was added and reacted at 100°C for 1 hour to obtain an additive.

Synthesis example 3 dinonylphenol (BO)! . [30 mol adduct of dinonylphenol with 1,2-butylene oxide] 1.
6 mol and 1 mol of MDI in the same manner as in Synthesis Example 1.
After reacting at 0°C for 11 hours, 0.6 mol of diethylamine was added and reacting at 60°C for 1 hour to obtain an additive.

Synthesis Example 4 Dodecylphenol (BO) + s (15 mol adduct of dodecylphenol with 1,2-butylene oxide) 1.5
60 mol and 1 mol of MDI in the same manner as in Synthesis Example 1.
After reacting at °C for 11 hours, 0.5 mole of 15 mole adduct of 1,2-butylene oxide of N,N-dimethylaminopropylamine (BO) + sCN,N-dimethylaminopropylamine] was added, and the mixture was heated to 60 °C. The mixture was reacted for 1 hour to obtain an additive.

Synthesis Example 5 Oleyl alcohol (BO) to (20 mol adduct of oleyl alcohol with 1,2-butylene oxide) 1
．． After reacting 5 moles of MDI and 1 mole of MDI at 60°C for 1 hour in the same manner as in Synthesis Example 1, 0.5 moles of methylbiperazine was reacted.
5 mol was added and reacted at 60°C for 1 hour to obtain an additive.

Synthesis Example 6 Dodecylphenol (BO) r. (PO)+. [After adding 10 moles of 1,2-butylene oxide to dodecylphenol, 31.5 moles of a block adduct obtained by adding 10 moles of propylene oxide and 1 mole of TDI were reacted at 80°C in the same manner as in Synthesis Example 1. After that, 0.5 mol of piperazine was added and the mixture was reacted at 80°C for 1 hour to obtain an additive.

Synthesis Example 7 Oleic acid (BO) zs C 1.5 mol of 25 mol adduct of 1,2-butylene oxide of oleic acid and HD11
After reacting 100° C. for 611 hours in the same manner as in Synthesis Example 1, 0.5 mole of morpholine was added and the mixture was reacted at 100° C. for 1 hour to obtain an additive.

Synthesis Example 8 Dihydrogenated beef tallow amine (BO) Z. [Dihydrogenated beef tallow amine 1
, 2-butylene oxide 20 mol adduct] 2 mol and H
1 mole of Dl was added to 100°61 in the same manner as in Synthesis Example 1.
The additive was obtained by reacting for 2 hours.

Synthesis Example 9 1.5 mol of 2-octyldodecyl alcohol (BO) zs [25 mol adduct of 1,2-butylene oxide of 2-octyldodecyl alcohol] and 1 mol of HDl were mixed at 100° for 611 hours in the same manner as in Synthesis Example 1. After reacting,
Add 0.5 mol of 2-methylbiperazine and heat to 1 at 80°C.
After a period of reaction, an additive was obtained.

Synthesis Example 10 Isostearic acid (BO) z. [20 moles of 1,2-butylene oxide adduct of isostearic acid] 1 mole and dimethylaminopropylamine (PO)+.

(BO) ,. [After adding 10 moles of propylene oxide to dimethylaminopropylamine, 31 moles of a block adduct obtained by adding 10 moles of 1,2-butylene oxide and 1 mole of HDl were added to 10 moles of dimethylaminopropylamine in the same manner as in Synthesis Example 1.
The reaction was carried out for 0°012 hours to obtain an additive.

Synthesis Example 11 Oleylamine (BO) Is (1.2 of oleylamine
Butylene oxide 15 mol adduct] 1.5 mol and HD
After reacting 1 mol of 1 mol at 100°C for 1 hour in the same manner as in Synthesis Example 1, 0.5 mol of 2-methylpiperazine was added and the reaction was carried out at 60°C for 1 hour to obtain an additive.

Comparative Synthesis Example 1 An additive was obtained by reacting a chloroformate of dodecylphenol (BO) zs (25 mol adduct of dodecylphenol with 1,2-butylene oxide) and ethylenediamine.

Comparative Synthesis Example 2 1.5 mol of oleyl alcohol and 1 mol of MDI in 6
After reaction at 0°C, 0.5 mol of diethylamine was added at 60°C.
The mixture was reacted for 1 hour to obtain an additive.

Example 1 A dispersibility test was conducted by the following method to examine the sludge deposition prevention and removal effects of the additives obtained in Synthesis Examples 1 to 11 and Comparative Synthesis Examples 1 to 2.

The hexane-insoluble, chloroform-soluble portion of the sludge scraped from the crankcase of an engine after high mileage driving was added as a chloroform solution to typical regular gasoline containing the test additives to give a sludge concentration of 600 ppm. Additive concentration to 1100pp
, 200 ppm, and 400 ppm, and the amount of sludge was examined 30 minutes after adding the sludge solution.

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

The results are shown in Table 1.

Table Example 2 A thermal decomposition test was conducted using the method described below to determine whether the additive itself would be deposited in the combustion chamber.

Approximately 1 g of the additive sample (50% kerosene solution) was accurately weighed, placed in a weighed aluminum cup, heated in a constant temperature bath at 200°C for 215 hours, and the remaining weight was measured. The decomposition rate was calculated using the following formula, using the weight of the additive sample as -i and the remaining weight as the needle.

Decomposition rate (χ) = (Wi −Wr−Wi/2)/(W
i/2) X100 The appearance of the residue was also observed with the naked eye.

The results obtained are shown in Table 2.

Table 2 Example 3 One tank (61f) of gasoline containing 1% by weight of gasoline additive was run on a general road, and the intake system (intake valve, intake port), combustion chamber, and carburetor intake before and after the test. The condition of the valves was evaluated by disassembling the engine and visually checking the degree of deposit removal. The test car is Toyota Carina 1800cc.
(engine type Is).

The degree of deposit removal before and after the test was judged based on the following criteria.

The results are shown in Table 3.

〔Effect of the invention〕

Compared to comparative products, the gasoline additive of the present invention has excellent sludge dispersion power and thermal decomposition properties, and also has excellent ability to clean the fuel intake system and combustion chamber in evaluations in actual vehicle tests.

Claims (1)

[Scope of Claims] 1. a) an alkylene oxide adduct having 2 to 6 carbon atoms of an aliphatic alcohol, an alkylphenol, a carboxylic acid, or an amine; and b) an aliphatic amine or an alicyclic or heterocyclic amine. A gasoline additive characterized by containing a reaction product of one or more compounds selected from the group and c) a polyisocyanate having two or more isocyanate groups. 2, a) A compound represented by the following general formula (1), and R-
X-(AO)_m-H...(1) [Here, R is an aliphatic hydrocarbon residue having 6 to 36 carbon atoms or an alkylphenyl group, or one or more nitrogen atoms or oxygen atoms represents an aliphatic hydrocarbon residue having -O-
, -CO-O-, -NR'-, or -N[(AO)_n
H]-, A represents an alkylene group having 2 to 6 carbon atoms, m and n are integers of 1 to 50, and R' represents a hydrocarbon residue having 1 to 22 carbon atoms. ] b) one or more compounds selected from the group of aliphatic amines having 1 to 3 nitrogen atoms, or alicyclic or heterocyclic amines, and c) two or more isocyanate groups. A gasoline additive characterized by containing a reactant with a polyisocyanate.