JPH06184568A - Gasoline composition - Google Patents

Abstract

The invention provides a gasoline composition comprising a major amount of a gasoline suitable for use in spark-ignition engines, a minor amount of a polyalphaolefin having a viscosity at 100 DEG C in the range 2 x 10<-><6> to 2 x 10<-><5> m<2>/s (2 to 20 centistokes), being a hydrogenated oligomer containing 18 to 80 carbon atoms derived from at least one alphaolefinic monomer containing from 8 to 16 carbon atoms, and a minor amount of a polyoxyalkylene compound selected from glycols, mono- and diethers thereof, having number average molecular weight (Mn) in the range 400 to 3000, the weight ratio polyalphaolefin: polyoxyalkylene compound being in the range 1:10 to 10:1; a concentrate for the preparation of such gasoline composition and a method of operating a spark-ignition engine using such gasoline composition.

Description

Detailed Description of the Invention

[0001]

This invention relates to a gasoline composition comprising a major amount of gasoline and a minor amount of at least one additive suitable for use in a spark ignition engine, and to prepare such a gasoline composition. Therefore, it relates to an additive concentrate suitable for addition to gasoline.

[0002]

2. Description of the Prior Art EP-A-290 088 discloses a major amount of gasoline suitable for use in spark ignition engines and 10
Viscosity at 0 ℃ is 2 × 10 ^-6 m ² / s to 2 × 10 ^-5
m ² / s (2 centistoke to 20 centistoke)
A small amount of polyalpha-olefin [preferably a hydrogenated oligomer containing 18 to 80 carbon atoms derived from an alpha-olefinic monomer containing 8 to 12 carbon atoms. And optionally, a small amount of an oil-soluble aliphatic polyamine and / or an alkali metal salt or alkaline earth metal salt and / or number of a succinic acid derivative having a polyolefin substituent on at least one carbon atom. Average molecular weight (M _n ) 500 to 15
Disclosed is a gasoline composition comprising a polyolefin derived from C ₂ to C ₆ monomers in the range of 00.

US Pat. No. 3,901,665 describes A. A major amount of liquid hydrocarbon fuel consisting of hydrocarbons boiling in the gasoline boiling range, and B. About 0.01 weight percent to about 0.06 weight percent, about 400 to about 1400, preferably about 400.
A 3-carbon or 4-carbon olefin having a molecular weight of from about 900 to about 900, preferably polyisobutylene and C.I. From about 0.008 weight percent to about 0.016 weight percent of the general formula

[0004]

[Chemical 1]

(Where R is from 1 to 20 carbon atoms)
Represents, preferably 10 to 18 alkyl groups,
x has an average value of 4 to 20) and is characterized in that the additive composition consists essentially of B and C and is characterized by improved deicing and carburetor cleaning power. A hydrocarbon fuel composition is disclosed.

US Pat. No. 3,658,494 discloses a fuel composition comprising a combination of at least one normally liquid major amount of fuel and a minor amount of additives soluble in the fuel. This additive combination is characterized by (a) at least one oxy compound which is a monoether of glycol or polyglycol, and (b) the presence of at least 30 aliphatic carbon atoms in the acyl group. At least one selected from the group consisting of at least one substantially saturated carboxylic acid ester, amide, imide, amidine and amine salt;
Of a fuel soluble dispersant, and the weight ratio of oxy compound to dispersant is about 0.1: 1 to about 1: 0.1, preferably 0.1: 1 to about 2.5: 1. The oxy compound used in the examples is ethylene glycol mono-
n-butyl ether, dipropylene glycol monomethyl ether, triethylene glycol monoethyl ether, and ethylene glycol monophenyl ether.

EP-A-384 605 describes a mixture of hydrocarbons boiling in the gasoline boiling range and also (i) the reaction product of a defined hydrocarbyl-substituted dibasic acid with a defined polyoxyalkylenediamine, (ii). ) C
_2-10 hydrocarbon polyolefin polymers, copolymers, corresponding aminated or hydrogenated polymers or copolymers, or mixtures thereof (wherein the polyolefin polymer or copolymer is in the range of 500 to 10,000) A polymerized component having a molecular weight), (iii) a polyalkylene glycol having a molecular weight in the range of 500-2000, and (iv)
A motor fuel composition comprising a lubricating oil is disclosed.
In connection with (ii), the olefin monomer from which the polyolefin polymer component is usually prepared is preferably an unsaturated C
It is described as a _2-6 hydrocarbon (page 9, 3)
(Lines 9, 40). Polyalkylene glycol (iii)
Are preferably selected from the group consisting of polyethylene glycol, polypropylene glycol and polybutylene glycol (pages 10, 39, 40).
line).

[0008] EP-A-526129 (published February 3, 1993) is, (i) the reaction product of a polyamine and (ii) at least one acyclic hydrocarbyl substituted succinic acylating agent and, Not Disclosed is a fuel additive concentrate comprising a hydrotreated poly-α-olefin for suppressing an increase in octane requirement in an internal combustion engine.
EP-A-526 129 further describes the reaction formation of a small but effective amount of (a) (i) a polyamine and (ii) at least one acyclic hydrocarbyl substituted succinic acylating agent. A fuel additive which comprises (b) an unhydrogenated poly-alpha-olefin having a volatility of less than about 50% as measured by the test method described herein, (c) and optionally added. , (A) a mineral oil having a viscosity index of less than about 90 and a volatility of 50% or less as measured by the test method described herein, (B) an antioxidant, or (C) a demulsifier, or (D) aromatic hydrocarbon solvent or (E) corrosion inhibitor, or component (A),
Two or three of (B), (C), (D) and (E),
A detailed description is given of a major amount of gasoline boiling range hydrocarbons or hydrocarbon / oxygenate mixtures or fuel compositions comprising oxygenates, containing four or all five combinations. Obviously, the essential feature is that the poly-α-olefin is an unhydrogenated poly-α-olefin. As the demulsifier (c), polyoxyalkylene glycols,
Included are oxyalkylated phenolic resins, and especially mixtures thereof.

[0009]

Surprisingly, the present inventors have found that gasoline containing a combination of a specific poly-α-olefin and a specific polyoxyalkylene glycol derivative has an engine intake system deposit amount of 50%. It has also been found that engine performance is surprisingly enhanced from the viewpoint of an advantageous combination condition of minimizing the amount of valve sticking.

[0010]

According to the present invention, a major amount of gasoline suitable for use in a spark ignition engine and 8
A hydrogenated oligomer containing 18 to 80 carbon atoms derived from at least one alpha-olefinic monomer containing 1 to 16 carbon atoms,
Viscosity at 100 ° C is 2 × 10 ^-6 m ² / s to 2 × 1
A small amount of polyalphaolefin in the range of 0 ^-5 m ² / s (2 to 20 centistokes); a number average molecular weight in the range of 400 to 3000 selected from glycols, their monoesters and diesters ( M
A gasoline composition comprising a small amount of a polyoxyalkylene compound having _n ), wherein the weight ratio of polyalphaolefin: polyoxyalkylene compound is in the range of 1:10 to 10: 1. A composition is provided.

The polyalphaolefins used in the gasoline composition of the present invention are predominantly trimers, tetramers and pentamers; synthesis of such materials is described by Campen et al., "Growing use of synlubes", Hydrocarbon. Process
Ing, February 1982, pages 75-82. The polyalpha-olefins are preferably derived from alpha-olefinic monomers containing 8 to 12 carbon atoms. Polyalphaolefins derived from decene-1 have been found to be very effective. The polyalphaolefin is preferably from 6 × 10 ⁻⁶ m ² / s to 1 × at 100 ° C.
The viscosity is in the range of 10 ⁻⁵ m ² / s (6 centistokes to 10 centistokes). 8 × 10 at 100 ° C
It has been found that polyalphaolefins having a viscosity of ^-6 m ² / s (8 centistokes) are very effective.

The polyoxyalkylene compound has the general formula R ¹ —O— (R—O) _n —R ² (I) (wherein R ¹ and R ² are independently a hydrogen atom or a hydrocarbyl group, preferably C _1-40 hydrocarbyl, such as an alkyl group, a cycloalkyl group, a phenyl group or an alkylphenyl group, each R independently represents an alkylene group,
Preferably, it represents a C _2-8 alkylene group, and n represents a polyoxyalkylene compound having M _{n in the range} of 400 to 3000, preferably 700 to 2000, more preferably 1000 to 1500).

Preferably, R ¹ represents a C _8-20 alkyl group and R ² represents a hydrogen atom. R ¹ is preferably C
_{It represents} a _10-18 alkyl group, more preferably a _C12-15 alkyl group. R ¹ may conveniently be a mixture of C _12-15 alkyl groups.

In the general formula I, the R group is preferably 1,
It is a 2-alkylene group.

Preferably, each R group independently represents a C _2-4 alkylene group, such as an ethylene group or a 1,2-propylene group. Very effective results have been obtained with polyalkylene compounds in which each R group represents a 1,2-propylene group.

The polyalphaolefin and the polyoxyalkylene compound are 100 ppmw to 1200 ppmw, preferably 100 ppmw to 60, based on the total composition.
0 ppmw, more preferably 150 ppmw to 500
Both can be advantageously present in amounts in the ppmw range.

The weight ratio of polyalphaolefin: polyoxyalkylene compound in the gasoline composition is preferably in the range of 1: 8 to 8: 1, more preferably 1: 5 to 5: 1. It has been found that weight ratios from 1: 4 to 4: 1 are very effective.

The gasoline composition of the present invention also preferably contains a small amount of at least one hydrocarbon soluble ashless dispersant. Compounds useful as ashless dispersants are generally characterized by "polar" groups attached to the relatively high molecular weight hydrocarbon chains. A "polar" group generally contains one or more of the elements nitrogen, oxygen and phosphorus. The solubilizing chains are generally of high molecular weight compared to those used with the metallic type, but in some cases are very similar.

Generally, ashless dispersants known to those skilled in the art for lubricant and fuel applications can be used in the gasoline compositions of the present invention.

In one embodiment of the present invention, the dispersant comprises: (i) at least one hydrocarbyl-substituted amine wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms; ii) having a hydrocarbon-based substituent of at least 10 aliphatic carbon atoms prepared by reaction of a carboxylic acylating agent with at least one amino compound containing at least one —NH— group. At least one acylated, nitrogen-containing compound, wherein the acylating agent is linked to the amino compound by an imide bond, an amide bond, an amidine bond, or an acyloxyammonium bond; (iii) at least one At least one nitrogen compound of a phenol compound, an aldehyde compound and an amino compound having a -NH- group of A concentrate; (iv) at least one substituted carboxylic acid ester; (v) at least one polymeric dispersant; (vi) at least one hydrocarbon-substituted phenolic dispersant; and (vii) at least one, It is selected from the group consisting of fuel soluble alkoxylated derivatives of alcohols, phenols or amines.

The hydrocarbyl substituted amines used in the gasoline composition of the present invention are well known to those skilled in the art and have been described in numerous patents. Among them are U.S. Patents 3,275,554, 3,438,757, 3,4.
54,555, 3,565,804, 3,755,
433 and 3,822,209. These patents disclose hydrocarbyl substituted amines suitable for use in the present invention, including methods of making.

Representative hydrocarbyl-substituted amines have the general formula: [AXN] _x [-N ([-UN-] _a [-UQ] _b )] _y R ³ _c H _{1 + 2y + ay- c} (II) (wherein A represents hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or a hydroxyhydrocarbyl group having 1 to 10 carbon atoms; X represents hydrogen, 1 to 10) Hydrocarbyl groups of 1 carbon atom, or 1 to 1
Represents a hydroxyhydrocarbyl group of 0 carbon atoms,
A and N together with 5 to 6 ring members can form a ring of up to 12 carbon atoms; U represents an alkylene group of 2 to 10 carbon atoms, Included therein are the hydrocarbons required to position the valency nitrogen;
R ³ represents an aliphatic hydrocarbon of 30 to 400 carbon atoms; Q is a piperazine structure; a is an integer of 0 to 10; b is an integer of 0 to 1 ;
a + 2b is an integer of 1 to 10; c is 1 to 5
An average of 1 to 4 and less than or equal to the number of nitrogen atoms in the molecule; x is an integer of 0 to 1; y is an integer of 0 to 1; x + y Is equal to 1).

In interpreting this general formula, it is natural that the R ³ and H atoms are attached to the insufficient nitrogen valence within the brackets of the general formula. Thus, for example, this general formula includes derivatives where R ³ is attached to the terminal nitrogen and isomeric derivatives where R ³ is attached to the non-terminal nitrogen atom. R
Nitrogen atoms not bound to ³ can give rise to hydrogen or AXN substituents.

Hydrocarbyl-substituted amines useful in the present invention and encompassed by general formula II above include poly (propylene) amine, N, N-dimethyl-n-poly (ethylene / propylene) amine (monomeric 50:50
Molar ratio), poly (isobutene) amine, N, N-di (hydroxyethyl) -N-poly (isobutene) amine, poly (isobutene / 1-butene / 2-butene) amine (monomer 50:25: 25 molar ratio), N- (2-hydroxyethyl) -N-poly (isobutene) amine, N- (2
Monoamines such as -hydroxypropyl) -N-poly (isobutene) amine, N-poly (1-butene) aniline and N-poly (isobutene) -morpholine, and N-
Poly (isobutene) ethylenediamine, N-poly (propylene) trimethylenediamine, N-poly (1-butene) diethylenetriamine, N ', N'-poly (isobutene) tetraethylenepentamine, N, N-dimethyl-
Mention may be made of N'-poly (propylene) and polyamines such as 1,3-propylenediamine.

Hydrocarbyl-substituted amines useful in the gasoline composition of the present invention also include specific N-amino-hydrocarbylmorpholines of the general formula: R ³ N (A) UM (III) (wherein R ³ is an aliphatic hydrocarbon group of 30 to 400 carbons, A is hydrogen, a hydrocarbyl group of 1 to 10 carbon atoms, or 1 to 10) Is a hydroxyhydrocarbyl group of carbon atoms, U is an alkylene group of 2 to 10 carbon atoms, and M is a morpholine structure). These hydrocarbyl substituted aminohydrocarbyl morpholines and polyamines represented by general formula II are representative hydrocarbyl substituted amines used in preparing the compositions of the present invention.

Numerous acylated, nitrogen-containing compounds with hydrocarbon-based substituents of at least 10 aliphatic carbon atoms prepared by the reaction of carboxylic acylating agents with amino compounds are known to those skilled in the art. It is well known. The acylating agent is bonded to the amino compound through an imide bond, an amide bond, an amidine bond or an acyloxyammonium bond. The hydrocarbon-based substituent of at least 10 aliphatic carbon atoms may be either in the carboxylic acylating agent-derived portion of the molecule or in the amino compound-derived portion of the molecule. However, it is preferably in the acylating agent moiety. The acylating agent is 5,000, 10,000 or 20, from formic acid and its acylated derivative.
Various acylating agents having high molecular weight aliphatic substituents of up to 000 carbon atoms can be used. Various amino compounds can be used, from ammonia itself to amines having an aliphatic substituent of up to 30 carbon atoms.

A representative system of acylated, nitrogen-containing compounds useful in the compositions of the present invention is an acylating agent having an aliphatic substituent of at least 10 carbon atoms and at least one-. It is prepared by reaction with a nitrogen compound characterized by the presence of an NH-group. Typically, the acylating agent is a monocarboxylic acid or polycarboxylic acid (or a reaction equivalent thereof) such as a substituted succinic acid or propionic acid, and the amino compound is a polyamine or a mixture of polyamines, most typically Typically, it is a mixture of ethylene polyamines. The amine may also be a hydroxyalkyl substituted polyamine. The aliphatic substituents in such acylating agents preferably have an average of at least 30 or 50 to 400 carbon atoms.

Specific examples of hydrocarbon-based substituents containing at least 10 aliphatic carbon atoms are n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, chlorooctadecyl and triicontanyl. is there. Generally, the hydrocarbon-based substituents are monoolefins and diolefins alone, having from 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1-hexene and 1-octene. It is produced from a polymer or a multicomponent copolymer (for example, a copolymer or a terpolymer). Typically, these olefins are 1-monoolefins.
Also, the substituents can be derived from halogenated (eg, chlorinated or brominated) analogs of such homopolymers or multicomponent copolymers. However, the substituents may be monomeric high molecular weight alkenes (eg 1-tetracontene), chlorinated analogues and their chlorinated analogues, aliphatic petroleum fractions, especially paraffin waxes, their cracked analogues, chlorinated analogues. Analogs and chlorinated analogs, white oils, synthetic alkenes such as those produced by the Ziegler-Natta process (eg,
It can be made from other materials such as poly (ethylene) grease, as well as other materials known to those skilled in the art. Unsaturation within substituents can be reduced or eliminated by hydrogenation according to techniques well known to those skilled in the art.

As used herein, "hydrocarbon-based" refers to a group having a carbon atom directly attached to the residue of the molecule and having the predominantly hydrocarbon character within the scope of this invention. Thus, a hydrocarbon-based group can contain up to one non-hydrocarbon group for every ten carbon atoms provided that the non-hydrocarbon group does not significantly alter the group's predominantly hydrocarbon character. One of ordinary skill in the art will recognize such groups including, for example, hydroxyl groups, halo groups (especially chloro and fluoro groups), alkoxyl groups, alkylmercapto groups and alkylsulfoxy groups. However, hydrocarbon-based substituents are usually purely hydrocarbyl and do not contain such non-hydrocarbyl groups.

Hydrocarbon-based substituents are substantially saturated, that is, they contain no more than one carbon-carbon unsaturated bond for every 10 carbon-carbon single bonds present. It usually contains no more than one carbon-carbon non-aromatic unsaturated bond for every 50 carbon-carbon bonds present.

Further, the hydrocarbon-based substituent is essentially aliphatic in its nature. That is, it contains no more than 1 non-aliphatic moiety (cycloalkyl, cycloalkenyl or aromatic) group of 6 carbon atoms or less for every 10 carbon atoms in the substituent. Usually, however, a substituent will contain no more than one such non-aliphatic group for every 50 carbon atoms, and in many cases will contain no such non-aliphatic group, ie, a typical substitution. The group is purely aliphatic. Typically these purely aliphatic substituents are alkyl or alkenyl groups.

Examples of substantially saturated hydrocarbon-based substituents containing an average of more than 30 carbon atoms include:
Mixtures of poly (ethylene / propylene) groups of 35 to 70 carbon atoms, oxidatively or mechanically decomposed poly (ethylene / propylene) of 35 to 70 carbon atoms
There are mixtures of groups, mixtures of poly (propylene / 1-hexene) groups of 80 to 150 carbon atoms, and mixtures of polyisobutene groups having an average of 50 to 75 carbon atoms.

The preferred material for the substituents is a C ₄ refinery having a butene content of 35 to 75 weight percent and an isobutene content of 30 to 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. It is a polyisobutene obtained by polymerizing a distillate. These polyisobutenes are primarily (80% of total repeating units) isobutene repeating units _{constituting: -C (CH 3) 2 CH} 2 - containing.

Representative of amino compounds useful in the preparation of these acylated compounds are: (1) Polyalkylene polyamines of the general formula: (R ⁴ ) ₂ N [P- N (R ⁴ )] _m R ⁴ (IV) (wherein each R ⁴ independently represents a hydrogen atom, a hydrocarbyl group containing up to 30 carbon atoms or a hydroxy-substituted hydrocarbyl group, but at least one R 4 ⁴ represents a hydrogen atom, m is an integer from 1 to 10, and P
Represents a C _1-18 alkylene group), (2) hydroxyalkyl-substituted polyamines in which polyamines are as described above, (3) polyamines are as described above, and heterocyclic substituents are, for example, piperazine. , Imidazoline, pyrimidine or morpholine, and heterocyclic-substituted polyamines, and (4) aromatic polyamines having the following general formula: Ar (NR ⁴ ₂ ) _z (V) (where Ar is An aromatic nucleus of 6 to 20 carbon atoms, each R ⁴ is as defined above, z
Is 2 to 8).

Specific examples of the polyalkylene polyamines represented by the general formula IV include ethylenediamine, tetra (ethylene) pentamine, tri- (trimethylene) -tetraamine and 1,2-propylenediamine.

Specific examples of hydroxyalkyl-substituted polyamines include N- (2-hydroxyethyl) ethylenediamine and N, N'-bis- (2-hydroxyethyl).
Mention may be made of ethylenediamine and N- (3-hydroxybutyl) tetramethylenediamine.

Specific examples of the heterocyclic substituted polyamines include N-2-aminoethylpiperazine, N-2-aminopropylmorpholine and N-3-aminopropylmorpholine, N-3- (dimethylamino) propylpiperazine, 2-heptyl-3- (2-aminopropyl) imidazoline, 1,4-bis (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) piperazine, and 2
-Heptadecyl-1- (2-hydroxyethyl) -imidazoline.

Specific examples of aromatic polyamines include:
Included are various isomeric phenylenediamines and various isomeric naphthalenediamines.

US Pat. Nos. 3,172,892, 3,219,666, 3,272,746, 3,3
10,492, 3,341, 542, 3,444,
170, 3,455,831, 3,455,83
2, 3,576,743, 3,630,904, 3,632,511, 3,804,763 and 4,
A number of patents, including 234,435, describe useful acylated nitrogen compounds. Typical acylated nitrogen-containing compounds in this system have from 50 to 4 polyisobutene substituents.
It is prepared by reacting a polyisobutene-substituted succinic anhydride acylating agent having 00 carbon atoms with a mixture of ethylene polyamines having 3 to 7 amino nitrogen atoms per ethylene polyamine.

Another type of acylated nitrogen compound belonging to this system is a combination of the above-mentioned alkylene amines with the above-mentioned substituted succinic acid or succinic anhydride and an aliphatic monocarboxylic acid having 2 to 22 carbon atoms. It is produced by a reaction. The molar ratio of succinic acid to monocarboxylic acid in these types of acylated nitrogen compounds ranges from 1: 0.1 to 1: 1. As a representative of monocarboxylic acid,
There are commercially available mixtures of stearic acid isomers known as formic acid, acetic acid, dodecanoic acid, butanoic acid, oleic acid, stearic acid, isostearic acid, and triacrylic acid. Such materials are described in detail in US Pat. Nos. 3,216,936 and 3,250,715.

Another type of acylated nitrogen compound useful in the gasoline composition of the present invention is an aliphatic monocarboxylic acid of 12 to 30 carbon atoms and the above alkylene amines, typically 2 to Reaction products with ethylene polyamines, propylene polyamines or trimethylene polyamines containing 8 amino groups and mixtures thereof. The aliphatic monocarboxylic acid is usually a mixture of straight and branched chain aliphatic carboxylic acids containing 12 to 30 carbon atoms. Widely used forms of acylated nitrogen compounds include the above alkylene polyamines and 5 to 30 mole percent straight chain fatty acids and 70 mole percent.
It is prepared by reaction with a mixture of fatty acids having a mole percent to 95 mole percent branched chain fatty acids. It is widely known to the person skilled in the art as isostearic acid in commercially available mixtures. These mixtures are described in U.S. Pat. Nos. 2,812,342 and 3,26.
It is prepared as a by-product from the dimerization of unsaturated fatty acids as described in US Pat.

Branched chain fatty acids can also include those where the branching is not essentially alkyl, such as found in phenyl and cyclohexyl stearic acid and chlorostearic acid. Branched chain aliphatic carboxylic acid / alkylene polyamine products are described, for example, in US Pat. No. 3,110,67.
3, 3,251,853, 3,326,801, 3,337,459, 3,405,064, 3,4
29,674, 3,468,639, and 3,85
7, 791.

Phenol / aldehyde / amino compound concentrates useful as dispersants in the gasoline compositions of the present invention include those commonly referred to as Mannich concentrates. Generally, these are at least one bound to an aromatic carbon.
Hydrocarbon-substituted phenols having 4 hydrogen atoms (eg, at least 12 to 400 alkyl groups on average,
At least one active hydrogen compound such as an alkylphenol, preferably having from 30 to 400 carbon atoms), at least one aldehyde or aldehyde-generating substance (typically a formaldehyde precursor) and at least one NH group Prepared by simultaneous or sequential reaction with at least one amino compound or polyamino compound having Amino compounds include hydrocarbon substituents of 1 to 30 carbon atoms or 1 to 30
Primary or secondary monoamines having a hydroxyl-substituted hydrocarbon substituent of 4 carbon atoms are mentioned. Another type of representative amino compound is the polyamines mentioned in the discussion of acylated nitrogen-containing compounds.

Representative examples of monoamines include methylethylamine, methyloctadecylamines, aniline, diethylamine, diethanolamine and dipropylamine. The following patent has an extensive description of Mannich concentrates: US Pat. No. 2,459,11.
2, 3,413,347, 3,558,743, 2,962,442, 3,442,808, 3,5
86,629, 2,984,550, 3,448,
047, 3,591,598, 3,036,00
3, 3rd, 454, 497, 3rd, 600, 372, 3rd, 166, 516, 3rd, 459, 661, 3rd, 6th
34,515, third 3,236,770, third 461,
172, third 3,649,229, third 3,649,22
9, 3,355,270, 3,493,520, 3,697,574, 3,368,972 and 3,
539,633.

Concentrates produced from sulfur-containing reactants can also be used in the gasoline composition of the present invention. For such sulfur-containing concentrates, see US Pat.
368,972, 3,649,229, 3,60
0,372, 3,649,659 and 3,741,
896. These patents also disclose sulfur-containing Mannich concentrates. Generally, the concentrates used in making the compositions of the present invention are made from phenols which yield alkyl substituents of 6 to 400 carbon atoms, more typically 30 to 250 carbon atoms.
Typical of these concentrates are formaldehyde or C _2-7
It is prepared from aliphatic aldehydes and amino compounds such as those used to prepare the acylated nitrogen-containing compounds described above.

These preferred concentrates are 1 mol of phenolic compound and 1 to 2 mol of aldehyde and 1 to 5 equivalents of amino compound (equivalents of amino compounds are the molecular weight divided by the number of = NH groups present). Is prepared). The conditions for carrying out such a concentration reaction are:
It is well known to those skilled in the art.

Particularly preferred systems of nitrogen-containing concentrates for use in the gasoline compositions of the present invention are (1) aliphatic based substituents or cycloaliphatic groups having at least 30 carbon atoms and at most 400 carbon atoms. Reacting at least one hydroxyaromatic compound containing a substituent based on a lower aliphatic C _1-7 aldehyde or a reversible polymer thereof at a temperature of up to 150 ° C. in the presence of an alkaline reagent such as an alkali metal hydroxide. , (2) substantially neutralizing the intermediate reaction mixture thus formed, and (3) reacting the neutralized intermediate with at least one compound containing an amino group having at least one -NH- group. It is manufactured by

More preferably, these concentrates are
(A) Phenols which give rise to hydrocarbon-based substituents having 30 to 250 carbon atoms, which substituents are derived from polymers of polypropylene, 1-butene, 2-butene or isobutene. And (b) formaldehyde or reversible polymers thereof (eg trioxane, paraformaldehyde) or functional equivalents thereof (eg methylol) and (c) alkylene polyamines such as ethylene polyamines having 2 to 10 nitrogen atoms. Manufactured.

Esters useful as dispersants in the gasoline composition of the present invention have at least 30, preferably at least 50 and at most 750 aliphatic carbon atoms whose substituents are substantially aliphatic. It is a derivative of a substituted carboxylic acid which is a group based on a substantially saturated hydrocarbon contained therein. As used herein, "hydrocarbon-based" refers to a group having a carbon atom directly attached to the residue of the molecule and having the predominant hydrocarbon character within the scope of this invention. Such groups include
The following may be mentioned: (1) Hydrocarbon groups; that is, aliphatic groups of the type known to those skilled in the art, aromatic- and alicyclic-substituted aliphatic groups and the like.

(2) Substituted hydrocarbon groups; that is, groups which, within the scope of the present invention, contain non-hydrocarbon substituents which do not alter the predominantly hydrocarbon character of the group. One of ordinary skill in the art will recognize the preferred substituents, such as halo, nitro, hydroxy, alkoxy, carboalkoxy and alkylthio groups.

(3) Hetero groups; that is, having the major hydrocarbon character within the scope of the invention and containing atoms other than carbon present in the chain or ring (ie in the chain or ring consisting of carbon atoms). Group to do. Preferred heteroatoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.

In general, no more than about 3 substituents or heteroatoms are present, preferably no more than 1 for each 10 carbon atoms in the hydrocarbon-based radical.

Substituted carboxylic acids are usually prepared by alkylation of unsaturated acids or their derivatives, such as their anhydrides, with materials of the preferred hydrocarbon-based group. Preferred unsaturated acids and their derivatives include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, glutaconic acid. , Chloromaleic acid, aconitic acid, crotonic acid, methylcrotonic acid, sorbic acid, 3-hexenoic acid, 10-decenoic acid and 2-pentene-1,3,5-tricarboxylic acid. Particularly preferred are unsaturated dicarboxylic acids and their derivatives, especially maleic acid, fumaric acid and maleic anhydride.

Preferred alkylating agents include homopolymers and multicomponent copolymers of polymerizable olefin monomers containing 2 to 10, usually 2 to 6 carbon atoms, and polar substituents thereof. Including derivatives. Such polymers are substantially saturated (ie, contain no more than about 5% olefinic bonds) and are substantially aliphatic (ie, of units derived from aliphatic monoolefins). At least 80% by weight, preferably at least 95
% By weight). Specific monomers that can be used to produce such polymers are ethylene, propylene, 1
-Butene, 2-butene, isobutene, 1-octene and 1-decene. Unsaturated units include conjugated dienes such as 1,3-butadiene and isoprene; 1,4-hexadiene, 1,4-cyclohexadiene, 5-ethylidene-
Non-conjugated dienes such as 2-norbornene and 1,6-octadiene; and 1-isopropylidene-3a, 4.
7,7a-Tetrahydroindene, 1-isopropylidene-dicyclopentadiene and 2- (2-methylene-4)
It can be derived from trienes such as -methyl-3-pentenyl) [2.2.1] -bicyclo-5-heptene.

The most preferred system of polymer is propylene,
It consists of terminal olefins such as 1-butene, isobutene and 1-hexene. Especially preferred in this system are the polybutenes which consist mainly of isobutene units. The second preferred system is ethylene and C _3-8 α-
It comprises a terpolymer of a mono-olefin with a polyene selected from the group consisting of (particularly preferred) non-conjugated dienes and trienes. Specific examples of these terpolymers include about 48 mole percent ethylene groups, 48 mole percent propylene groups and 4 mole percent 1,4-.
EI duPont de Ne which is a terpolymer containing a hexadiene group and having an intrinsic viscosity of 1.35 (8.2 g of the polymer dissolves in 10 ml of carbon tetrachloride at 30 ° C.).
“Ortholeum 2052” manufactured by mours & Company
Is.

Methods for preparing substituted carboxylic acids and their derivatives are well known to those skilled in the art and need not be described in detail. References include, for example, US Pat. No. 3,272,74.
6, third, 522, 179 and fourth, 234, 435. The molar ratio of polymer to unsaturated acid or derivative thereof may be equal, greater than 1 or less than 1, depending on the type of product desired.

Esters are esters of the abovementioned substituted carboxylic acids with hydroxy compounds which may be aliphatic compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols. Examples of aromatic hydroxy compounds include phenol and β-
Naphthol, α-naphthol, cresol, resorcinol, catechol, p, p′-dihydroxybiphenyl, 2-chlorophenyl, 2,4-dibutylphenol, propene tetramer-substituted phenol, didodecylphenol, 4,4′-methylene-bis- Phenol,
α-decyl-β-naphthol, polyisobutene (molecular weight 1000) substituted phenol, condensation product of heptylphenol and formaldehyde, condensation product of octylphenol and acetone, di (hydroxyphenyl) -oxide, di (hydroxyphenyl) ) Sulfide, di (hydroxyphenyl) disulfide and 4-cyclo-hexylphenyl. Phenols and alkylated phenols with up to 3 alkyl substituents are preferred. Each alkyl substituent can contain 100 or more carbon atoms.

Aliphatic alcohols from which the ester can be derived preferably contain up to 40 aliphatic carbon atoms. They are methanol, ethanol, isooctanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, β-phenylethyl alcohol, 2-methylcyclohexanol, β-. Chloroethanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monopropyl ether, triethylene glycol monododecyl ether, ethylene glycol monooleate, diethylene glycol monostearate, sexpentyl alcohol, tertbutyl alcohol, 5- Bromo-dodecanol, nitro-octadecanol and glycerol diole It may be a monohydric alcohol such as G. Polyhydric alcohols preferably contain 2 to 10 hydroxy groups. Specific examples thereof include, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tri-butylene glycol, and an alkylene group having 2 to 8 carbon atoms. Other alkylene glycols containing atoms are mentioned. Other useful polyhydric alcohols include glycerol, glycerol monooleate, glycerol monostearate, glycerol monomethyl ether,
Pentaerythritol, 9,10-dihydroxystearic acid, methyl ester of 9,10-dihydroxystearic acid, 1,2-butanediol, 2,3-hexanediol, 2,4-hexanediol, penacol,
Mention may be made of erythritol, arabitol, sorbitol, mannitol, 1,2-cyclohexanediol and xylene glycol. Also, carbohydrates such as sugars, starches and celluloses can give rise to the esters useful in the present invention. The carbohydrate may typically be glucose, fructose, sucrose, rhamnose, mannose, glyceraldehyde and galactose.

A particularly preferred system of polyhydric alcohols is a monocarboxylic acid in which some of the hydroxy groups have from 8 to 30 carbon atoms, such as octanoic acid, oleic acid, stearic acid, linolenic acid, dodecanoic acid or tall oil acid. It has at least 3 hydroxy groups which are esterified with an acid. Examples of such partially esterified polyhydric alcohols are sorbitol monooleate, sorbitol distearate, glycerol monooleate, glycerol monostearate, erythritol di-dodecanoate.

Esters can also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexen-3-ol and oleyl alcohol. Yet another system of alcohols capable of forming the esters useful in the present invention is, for example, oxyalkylene having at least one oxyalkylene group, oxyarylene group, amino-alkylene group or amino-arylene group. Substituted alcohols, oxyarylene substituted alcohols, amino-alkylene substituted alcohols and amino-
Consists of ether-alcohols and amino-alcohols including arylene-substituted alcohols. Typical of them are cellosolve, carbitol, phenoxyethanol, heptylphenyl- (oxypropylene) ₆
-H, octyl- (oxyethylene) _30- H, phenyl- (oxyoctylene) _2- H, mono (heptylphenyl-oxypropylene) -substituted glycerol, poly (styrene oxide), amino-ethanol, 3-aminoethyl -Pentanol, di (hydroxyethyl) amine, p-amino-phenyl, tri (hydroxypropyl) amine, N-hydroxyethylethylenediamine and N, N, N ', N'-tetrahydroxy-trimethylenediamine. Generally, ether-alcohols are preferred in which the alkylene group has up to about 150 oxyalkylene groups containing 1 to 8 carbon atoms.

The esters are diesters or acid esters of succinic acid, that is, partially esterified polyhydric alcohols or phenols, that is, esters having a free alcoholic hydroxy group or a phenolic hydroxy group. May be Mixtures of the above esters likewise fall within the scope of the present invention.

The succinate ester can be prepared by one of several methods. The preferred method, which is convenient and convenient for producing the ester of outstanding properties, involves the reaction of a suitable alcohol or phenol with a substantially hydrocarbon substituted succinic anhydride. Esterification is usually above about 100 ° C, preferably 150 ° C.
To 300 ° C.

Water formed as a by-product is removed by distillation as the esterification reaction proceeds. Solvents can be used for esterification to facilitate mixing and temperature control. It also facilitates the removal of water from the reaction mixture. Useful solvents include xylene, toluene, diphenyl ether, chlorobenzene and mineral oil.

A variant of the above method involves the replacement of the substituted succinic anhydride with the corresponding succinic acid. However, succinic acid readily dehydrates at temperatures above about 100 ° C. and is converted to their anhydrides which are esterified by reaction with alcohol reactants. In this respect, succinic acid is considered to be substantially equivalent to their anhydrides in this way.

The relative proportions of succinic and hydroxyreactants that can be used are highly dependent on the type of product desired and the number of hydroxyl groups present in the hydroxyreactant molecule. For example, the formation of half-esters of succinic acid, i.e. those in which only one of the two acid groups is not esterified, is associated with the use of one mole of monohydric alcohol for each mole of substituted succinic acid reactant, whereas The formation of the succinic acid diester involves the use of 2 moles of alcohol for each mole of acid. On the other hand, 1 mole of hexahydric alcohol binds equivalently to 6 moles of succinic acid to form an ester in which each of the alcohol's 6 hydroxyl groups is esterified with one of the 2 acid groups of succinic acid. Therefore, the maximum proportion of succinic acid to be used with the polyhydric alcohol is determined by the number of hydroxyl groups present in the molecule of the hydroxyreactant. The esters obtained by the reaction of equimolar amounts of succinic and hydroxyreactants have outstanding properties for the purposes of the present invention,
Therefore, it has been found to be preferable.

In some cases it is advantageous to carry out the esterification in the presence of a catalyst such as sulfuric acid, pyridine hydrochloric acid, hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, phosphoric acid or other well known esterification catalysts. The amount of catalyst in the reaction may be 0.01% by weight (based on the reaction mixture) but is usually 0.1% to 5% by weight.

In addition, succinic acid esters can be obtained by reacting a substituted succinic acid or its anhydride with an epoxide or with a mixture of epoxide and water.
Such a reaction is similar to that requiring an acid or its anhydride and a glycol. For example, the product can be prepared by reacting a substituted succinic acid with 1 mole of ethylene oxide. Similarly, the product is a substituted succinic acid and 2
It can be obtained by reaction with molar ethylene oxide. Other commonly available epoxides used in such reactions include, for example, propylene oxide, styrene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, cyclohexene oxide, 1,2 oxide. −
Octylene, epoxidized soybean oil, 9,10-epoxy-
Mention may be made of the methyl ester of stearic acid and butadiene mono-epoxide. Generally, epoxides have alkylene groups having 2 to 8 carbon atoms; or alkylene oxides having fatty acid groups having up to 30 carbon atoms;
Epoxidized fatty acid esters in which the ester group is derived from a lower alcohol having up to 4 carbon atoms.

Instead of succinic acid or its anhydride, a lactone acid or a substituted succinic acid halide can be used in the above method. Such acid halides may be acid dibromides, acid dichlorides, acid monochlorides and acid monobromides. Substituted succinic anhydrides and acids can be prepared, for example, by reacting maleic anhydride with high molecular weight olefins or halogenated hydrocarbons such as those obtained by chlorination of the olefin polymers described above. The reaction merely heats the reactant, preferably at a temperature of 100 ° C to 250 ° C. The product resulting from such a reaction is an alkenyl succinic anhydride. Alkenyl groups can be hydrogenated to alkyl groups. Anhydrous is
It can be hydrolyzed to the corresponding acid by treatment with water or steam. Other methods useful for the preparation of succinic acid or its anhydrides require the reaction of itaconic acid or its anhydrides with olefins or chlorinated hydrocarbons, usually at temperatures in the range 100 ° C to 250 ° C. The succinic acid halide can be prepared by reacting an acid or its anhydride with a halogenating agent such as phosphorus tribromide, phosphorus pentachloride or thionyl chloride. Various methods for preparing succinic acid compounds are well known to those skilled in the art and need not be discussed in further detail here.

Still other methods of preparing the esters useful in the gasoline compositions of the present invention are available. For example, the esters may be the reaction of a maleic acid or its anhydride as described above with an alcohol to form a monoester or diester of maleic acid, followed by the above-mentioned reaction of this ester with an olefin or chlorinated hydrocarbon. It can be obtained by such a reaction. It can also be obtained by first esterifying itaconic anhydride or itaconic acid under the same conditions as above and then reacting the ester intermediate with an olefin or a chlorinated hydrocarbon.

A number of different types of polymeric dispersants have been suggested to be useful in lubricating oil formation, and such polymeric dispersants are useful in the gasoline compositions of the present invention. It has always been stated that such additives are useful in lubricating formulation compositions as viscosity index improvers with dispersant properties. Polymerizing dispersants are usually polymers or copolymers having long chains of carbon and containing "polar" groups which impart dispersant properties. Examples of polar groups include amino, amide, imino, imide, hydroxyl and ether groups. For example, the polymerization dispersant may be a copolymer of methacrylates or acrylates containing additional polar groups, an ethylene / propylene copolymer having polar groups, or a vinyl acetate / fumarate ester copolymer. .

A number of such polymeric dispersants have been disclosed in the prior art, eg, US Pat. Nos. 4,402,844, 3,356.
763 and 3,891,721.

Many polymerization dispersants can also be prepared by grafting polar monomers onto the polyolefin skeleton. For example, U.S. Pat. No. 3,687,
849 and 3,687,905 describe the use of maleic anhydride as a grafting monomer on a polyolefinic backbone. Maleic acid or its anhydride is
Since this monomer is relatively inexpensive, it is economical to compound a nitrogen compound dispersant in the polymer by further reaction of the carboxyl group of maleic acid or its anhydride with, for example, a nitrogen compound or a hydroxy compound. It is particularly preferable as a graft monomer because it provides a simple route. U.S. Pat. No. 4,160,739 describes grafting a monomer system comprising maleic acid or its anhydride and at least one different monomer addition copolymerizable therewith, then the grafted monomer system. The graft copolymer obtained by the post-reaction with the above polyamine is described.
Since a considerably large amount of maleic acid or its anhydride can be included in the graft polymerization product, the monomer copolymerizable with maleic acid or its anhydride is sufficiently soluble in the reaction medium to give maleic acid or It is an α, β-monoethylenically unsaturated monomer that is reactive towards its anhydride. Thus, preferred monomers include acrylic acid and methacrylic acid esters, amides and nitriles, and monomers that do not contain free acid groups. For inclusion of the heterocyclic monomer in the graft polymer, a conjugated diene that is a hydrogenated block copolymer of styrene and has 4 to 6 carbon atoms to form the initial graft polymer. On the backbone copolymer, alone or in combination with styrene, graft-polymerized with an alkyl ester of acrylic acid or methacrylic acid. In the second step, the polymerizable heterocyclic monomer, alone or in combination with the hydrophobic vinyl ester, is copolymerized on the first graft copolymer to form the second graft copolymer. Form.

Other patents describing graft polymers useful as dispersants in the gasoline compositions of the present invention include US Pat. Nos. 3,243,481 and 3,47.
5,514, 3,723,575, 4,026,1
67, No. 4,085,055, No. 4,181,618 and No. 4,476,283.

Another system of polymeric dispersants useful in the gasoline compositions of the present invention is the so-called "star" polymers and copolymers. Such polymers are described in, for example, U.S. Pat. Nos. 4,346,193, 4,141,847, and 4,3.
58,565, 4,409,120 and 4,07
7, 893.

Hydrocarbon-substituted phenolic dispersants useful in the gasoline compositions of the present invention include hydrocarbon substituents
Included are hydrocarbon-substituted phenolic compounds having a molecular weight sufficient to render the phenolic compound soluble in the fuel. Generally, the hydrocarbon substituent is a substantially saturated hydrocarbon-based group having at least 30 carbon atoms. Phenolic compounds can be represented by normal following general _{^{formula: (R 5) e -Ar 1}} - (OH) f (VI) ( wherein, R ⁵ is an average 30 400 from aliphatic carbon Represents a substituent based on a substantially saturated hydrocarbon having atoms, e and f each represent 1, 2 or 3, and A
r ¹ represents an aromatic moiety such as a benzene nucleus, a naphthalene nucleus or a bonded benzene nucleus). The above phenates as represented by general formula VI can optionally contain other substituents such as lower alkyl groups, lower alkoxy groups, nitro groups, amino groups and halo groups. Preferred examples of the optional substituents are nitro group and amino group.

The substantially saturated hydrocarbon-based radical R ⁵ in the general formula VI can contain up to 750 aliphatic carbon atoms, but is usually at most 40 on average.
It has 0 carbon atoms. In some examples, R ⁵ is
It has a minimum of 50 carbon atoms. As mentioned above, the phenolic compound may contain more than one R ⁵ group for each aromatic nucleus in the aromatic moiety Ar ¹ .

The usually hydrocarbon-based radical R ⁵ is a monoolefin having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1-hexene and 1-octene. Derived from diolefin homopolymers or multicomponent copolymers (eg, copolymers, terpolymers). Typically, these olefins are 1-monoolefins. The R ⁵ group can also be derived from halogenated (eg, chlorinated or brominated) analogs of such homopolymers or multicomponent copolymers. However, the R ⁵ group is
High molecular weight alkenes (eg, 1-tetracontene),
Its chlorinated analogues and chlorinated analogues, aliphatic petroleum fractions,
Other materials such as paraffin waxes, their decomposed analogues, chlorinated and chlorinated analogues, white oils, synthetic alkenes such as those produced by the Ziegler-Natta process (eg poly (ethylene) grease) and , Can be manufactured from other materials known to those skilled in the art. Unsaturation within the R ⁵ group can be reduced or removed by hydrogenation by techniques well known to those skilled in the art prior to the nitrogenation step described below.

Substantially saturated hydrocarbon-based radical R ⁵
Specific examples of are: tetracontanyl groups, hempentacontanyl groups, mixtures of poly (ethylene / propylene) groups having 35 to 70 carbon atoms, 35
Of oxidatively or mechanically decomposed poly (ethylene / propylene) groups having 1 to 70 carbon atoms, 8
A mixture of poly (propylene / 1-hexene) groups having 0 to 150 carbon atoms, a mixture of polyisobutene groups having 20 to 32 carbon atoms and an average of 50 to 75 carbon atoms. A mixture of polyisobutene groups having.

A preferred material for the group R ⁵ is C having a butene content of 35 weight percent to 75 weight percent and an isobutene content of 30 weight percent to 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. Polyisobutenes obtained by polymerizing ₄ refinery fractions. These polyisobutenes are
Predominantly (> 80% of total repeat units) containing isobutene repeat building blocks.

[0080] _{-C (CH 3) 2 CH 2} - bond to the aromatic moiety Ar ¹ the radical R ⁵ hydrocarbon-based, can be made by a number of techniques well known to those skilled in the art.

In one preferred embodiment, the phenolic dispersants useful in the gasoline compositions of this invention are hydrocarbons of the general formula VI in which the optional substituent is at least one nitro group. Substituted nitrophenols.
Nitrophenols can be readily prepared by nitrating the preferred phenols, but typically at least 30 nitrophenols,
It is preferably formed by nitration of alkylphenols having an alkyl group of at least 50 carbon atoms. The preparation of a number of hydrocarbon substituted nitrophenols useful in the gasoline composition of the present invention is described in US Pat. No. 4,347,148.

In another preferred embodiment, the hydrocarbon-substituted phenol dispersants useful in the present invention are hydrocarbon-substituted amino such as those represented by general formula VI wherein the optional substituents are at least one amino group. It is a phenol. These aminophenols can be easily prepared by nitrating the preferred hydroxy aromatic compound as described above and then reducing the nitro group to an amino group. Typically, useful aminophenols are at least 30
Formed by nitration and reduction of alkylphenols having an alkyl or alkenyl group of 1, preferably at least 50 carbon atoms. The preparation of a number of hydrocarbon substituted aminophenols useful as dispersants in the present invention is described in US Pat. No. 4,320,021.

Also useful as dispersants in the gasoline composition of the present invention are fuel soluble alkoxylated derivatives of alcohols, phenols and amines. A variety of such derivatives can be utilized as long as the derivative is fuel soluble. Furthermore, the derivative is preferably water-insoluble in addition to being fuel-soluble. Thus, in a preferred embodiment, the fuel soluble alkoxylated derivative useful as a dispersant is characterized as having 1 to 13 HLB.

As known to those skilled in the art, the fuel-soluble and water-insoluble properties of alkoxylated derivatives are:
It can be controlled by the choice of the phenol or amine, especially the alkoxy reactant and the amount of the alkoxy reactant that reacts with the alcohol, phenol or amine. Thus, the alcohols used to prepare the alkoxylated derivatives are hydrocarbon-based alcohols whose amines are hydrocarbyl-substituted amines as described above. The phenols may be phenols or hydrocarbon-substituted phenols, and the hydrocarbon substituent may contain only one carbon atom.

The alkoxylated derivatives are obtained by reaction of alcohols, phenols or amines with epoxides or with mixtures of epoxides with water. For example, the derivative can be prepared by reacting an alcohol, phenol or amine with an equimolar amount or excess of ethylene oxide. Other epoxides capable of reacting with alcohols, phenols or amines include, for example, propylene oxide, styrene oxide, 1,2-butylene oxide, 2,2 oxide.
Mention may be made of 3-butylene, epichlorohydrin, cyclohexene oxide and 1,2-octylene oxide. Preferably, the epoxides are alkylene oxides whose alkylene group has 2 to 8 carbon atoms. As noted above, the amount of alkylene oxide that reacts with the alcohol, phenol or amine is preferably insufficient to render the derivative water soluble.

The following are examples of commercially available alkylene oxide derivatives that can be used as dispersants in the gasoline compositions of the present invention. Ethomeen S / 12, a tertiary amine ethylene oxide condensation product of primary aliphatic amines (HLB,
4.15; Armak Industries); and Plurafac A-24, BASF Wyando
tte industrial oxyethylated straight chain alcohol (HLB 5.0
). Other preferred fuel soluble alkoxylated derivatives of alcohols, phenols and amines will be readily apparent to those skilled in the art.

In a particularly preferred embodiment, the gasoline composition of the present invention comprises, in addition to the polyalphaolefin compound and the polyoxyalkylene compound, a polyolefin as _Mn 800 to 5000, preferably 1000 to ashless dispersant. 5000, more preferably at least 1750, 1800 or 1850 and at most 400
Small amounts of polyolefin substituted succinimide derivatives having 0, 3500, 3000 or 2500 can be included. The amine forming the succinimide is preferably a C _1-30 amine, in particular a C _4-12 amine containing 3 to 7 nitrogen atoms, eg diethylenetriamine, triethylenetetramine, tetramethylenepentamine, penta It is ethylene hexamine, hexaethylene heptamine, tripropylene tetramine and a mixture of two or more thereof.

Preferably, the hydrocarbon soluble ashless dispersant is preferably 30 ppmw to 500, based on the total composition.
It is present in an amount in the ppmw range, more preferably 100 ppmw to 300 ppmw.

Further, the gasoline composition may be (eg, instead of containing a succinimide derivative) EP-A-290 08.
8 oil-soluble polyamines or EP-A-41
N-substituted carbamates such as those described in 4963 can in each case be included in the same amounts as described above, based on the total composition.

Further, the gasoline composition contains, as a flame speed improver, an alkali metal salt or an alkaline earth metal salt of a succinic acid derivative as described in EP-A-290 088 in the same amount as the above with respect to the total composition. Can be included.

In addition to the components already mentioned above, the gasoline composition can also contain other additives. Thus, a lead compound can be included as an anti-knock additive, and thus the gasoline composition according to the present invention includes both leaded and unleaded gasoline. The gasoline composition also contains an antioxidant such as a phenolic resin such as 2,6-di-tert-butyl-phenol, or phenylenediamines such as N, N'-di-sec-butyl-p-phenylene-diamine. , Or anti-knock additives other than lead compounds, or eg US Pat. No. 4,477,261 and E.
Polyether amino additives such as those described in PA-151 621 may also be included.

The gasoline composition according to the invention comprises a major amount of gasoline (base fuel) suitable for use in spark ignition engines. This includes hydrocarbon base fuels that substantially boil in the gasoline boiling range 30 ° C to 230 ° C. These base fuels can consist of a mixture of saturated, olefinic and aromatic hydrocarbons. These can be derived from straight run gasoline, synthetically produced aromatic hydrocarbon mixtures, pyrolyzed or catalytically cracked hydrocarbon feedstocks, hydrolyzed petroleum fractions or catalytically reformed hydrocarbons. The octane number of the base fuel is not critical, but is usually above 65. The hydrocarbons in gasoline can be replaced to a large extent by alcohols, ethers, ketones or esters. Of course, it is desirable for the base fuel to be substantially free of water, as water interferes with successful combustion.

The polyalpha olefin compound and the polyoxyalkylene compound can be easily added as a formulation with other selected additives. Therefore, a convenient method of preparing a gasoline composition is to prepare a concentrate of polyalphaolefin compounds and polyoxyalkylene compounds with other additives to bring the concentrate to the required additive final concentration. This is a method of adding gasoline to the required amount.

Accordingly, the present invention further provides a gasoline compatible diluent, a polyalphaolefin as described above, a polyoxyalkylene compound as described above (polyalphaolefin: polyoxyalkylene compound weight ratio of 1:10 to 10). 1 range), and optionally at least one hydrocarbon-tolerant ashless dispersant, suitable for addition to gasoline.

Preferably, the polyalphaolefin and the polyoxyalkylene compound are present together in an amount ranging from 20% w to 80% w, and 5% when an ashless dispersant is present.
It is present in amounts ranging from w to 30% w (all percentages are relative to diluent).

Preferred gasoline compatible diluents are:
Hydrocarbons, for example alcohols or ethers such as heptane, methanol, ethanol, propanol, 2-butoxyethanol or methyl-tert-butyl ether. Preferably, the diluent is an aromatic hydrocarbon solvent such as toluene, xylene, mixtures thereof, or mixtures of toluene or xylene with alcohols. The solvent is preferably toluene. The concentrate can optionally include a defrosting agent, especially a polyether type ethoxylated alkylphenyl-formaldehyde resin. If a clouding agent is used, it can be present in the concentrate, preferably in an amount of 0.01% w to 2% w relative to the diluent.

In a further aspect, the present invention is a method of operating a spark-ignited internal combustion engine, which comprises introducing a gasoline composition according to the invention as described above into the combustion chamber of the engine. Provide the operation method of the engine.

[0098]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Shows the in various additives in the following Example: (a) "PGHE", the polymerization initiator was prepared using a mixture of C _12-15 alcohols as the range of M _n 1200 1500 of, ASTM 40 ° C according to D 445
Is a polyoxypropylene glycol hemiether (monoether) having a kinematic viscosity in the range of 72 mm ² / s to 82 mm ² / s available under the trade name "SAP 949" from the Royal Dutch / Shell group; (b ) “PAO” is 8 × 10 ^-6 m ² / s at 100 ° C
It is a polyalphaolefin which is a hydrogenated oligomer of decene-1 having a viscosity of (8 centistokes).

(C) "PMP" is a reaction between polyisobutylene having a number average molecular weight (M _n ) of 2470 (measured by quantitative reaction using ozone) and maleic anhydride,
Subsequently, the resulting polyisobutylene succinic anhydride and tetraethylenepentamine, pentaethylenehexamine and hexamethyleneheptamine (molar ratio 1: 2: 1).
40% w / w solution of polyisobutylene succinimide in xylene prepared by reaction [anhydride: amine molar ratio 2: 1] with a mixture of.

In the examples below, the amount of PMP is shown as the amount of solution, and when the amount of xylene is indicated, these are those without xylene associated with a 40% w / w solution of PMP. To do.

In the examples, the additive concentrate is PMP
Was prepared by adding PAO (and additional xylene) at 20 ° C. with stirring, followed by PGHE. Thereafter, a sample of these additive concentrates was added to the gasoline composition at the desired ingredient concentration with stirring. This reflects actual industrial practice and is important both for additive concentrates, which should be sufficiently stable, and for gasolines containing additives that give good properties in terms of engine cleaning and valve sticking prevention. Is.

Examples 1 to 8 Additive concentrates according to the invention and comparative examples were prepared as described above and stored for 6 weeks at 20 ° C. and -20 ° C., after which the stability was evaluated visually. The results are shown in Table I.

[0103]

[Table 1]

As can be easily seen, PHGE and PAO
The additive concentrate of the present invention containing both of the above showed good storage stability. On the other hand, the stability of the comparative example containing only PHGE was insufficient.

Examples 9 and 10 A standard VW Polo vehicle equipped with a single carburetor, 4-cylinder, 1.043 liter capacity engine was used to evaluate intake valve cleanliness in a road test sequence (Volkswagen Polo Road Test). .

Before the test, the intake parts and the combustion chamber were cleaned, a new pre-weighed intake valve and a new spark plug were fitted to the engine, a new oil filter was fitted and the engine was filled with fresh engine oil. A small windboard was attached to the roof of the test vehicle to increase wind resistance and therefore load the engine. Prior to running the 5000 km test distance, the fuel tank was emptied and filled with the test gasoline composition. Car 4500r
A 37 minute test cycle was used in which pm, 4th gear (105 kph) was run for 30 minutes and then allowed to idle for 7 minutes. For 12 consecutive cycles every day for 8 consecutive days, 5000
The test distance of km was passed. At the end of the test, the intake valve was removed and weighed to assess the average weight of the intake valve deposit.

The gasoline composition according to the present invention contains no additive (basic gasoline) or unleaded gasoline containing PMP and either or both of PHGE and PAO (9).
5 ULG) was subjected to a comparative test. The results are shown in Table II below.

[0108]

[Table 2]

The data in Table II show that the additive oil is PH
When the combination of GE and PAO (Examples 9 and 10), the amount of deposit on the intake valve was significantly more surprising than when the corresponding amount of additive oil consisted of either PHGE or PAO only. Is low.

Examples 11 to 23 A standard Opel Ascona 1.6 car from Ascona equipped with a standard 4-cylinder 1.6 liter 16SH engine was used for the evaluation of valve sticking according to the standard test method.

In the test method, the test gasoline composition was used to drive a car at a low duty cycle (maximum speed of 50 kph) on a regular street road over a total length of 130 km. Thereafter, the car was kept at -20 ° C overnight, the maximum compression pressure in each cylinder was measured, and the average of four values was calculated. The higher the pressure value, the better the result.

The "additive oil" is PHGE and / or PAO.
The composition of the test gasoline composition consisting of and the results obtained are shown in Table III below, in a manner similar to Table II.

[0113]

[Table 3]

It will be appreciated by those skilled in the art that the above concentrations represent three times the usual commercial concentrations in order to increase the severity of the test.

The above results show that the additive oil is PHGE and P.
In the case of the AO combination, the compression pressure results are very good, always markedly superior to PHGE alone and significantly better than the expected intermediate values of PHGE alone and PAO alone. It shows that it is roughly comparable to, and sometimes even superior to, PAO alone.

Examples 24 to 47 Effect of Gasoline Composition on Engine Intake System Deposits Induction system deposit simulator (I
SD) was evaluated by the test. In this test method, the gasoline composition was metered into a spray nozzle and expelled in a flat spray pattern onto the surface of an aluminum tube heated to 250 ° C. To promote the formation of deposits, the base gasoline used was old mixed pyrolysis gasoline. Under these test conditions, such base gasoline alone forms a carbonaceous deposit in the center of the tube surface. Detergency promoters prevent central area deposits and create ring-like deposits on the tube. Residual formations are evaluated visually by the following scale: 0-clean 1-2-close to clean 3-4-slightly carbonized 5-6-intermediate carbonization 7-8-intermediate to severe carbonization 9 -10-Severe carbonization Greater than 10-Very severe carbonization The results of the ISD test are shown in Table I below in a manner similar to Table III.
Shown in V.

[0117]

[Table 4]

[0118]

[Table 5]

The results in Table IV show that when the additive oil is a combination of PHGE and PAO, the ISD score is generally good and consistently superior to PAO alone, the expected values of PHGE alone and PAO. Significantly better than the median value of the single values, indicating that it can be roughly comparable to that of PHGE alone.

In conclusion, additive concentrates containing both PHGE and PAO have better storage stability compared to similar concentrates containing PHGE but no PAO; addition of PHGE and PAO in combination Gasoline containing additive oil was found to have lower intake valve deposits compared to where the additive oil was either PHGE or PAO; a combination of PHGE and PAO, as evidenced by compression pressure evaluation. Is significantly superior to PHGE alone in preventing valve sticking, and can be roughly comparable to PAO alone; as evidenced by ISD tests, prevention of deposit formation is greater than PAO alone in PHGE. It should be noted that the combination of PAO and PAO is remarkably predominant and can be generally comparable to PHGE alone.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Cornelis Juan Es, Kent Sea Tay 3/3 El G, Adhishiyam, Utzlands Road, Redd House

Claims (14)

[Claims] 1. A major amount of gasoline suitable for use in spark ignition engines; from 18 derived from at least one alpha olefinic monomer containing 8 to 16 carbon atoms. It is a hydrogenated oligomer containing 80 carbon atoms and has a viscosity of 2 × 10 at 100 ° C.
^-6 m ² / s to 2 × 10 ^-5 m ² / s (2 centistokes to 20 centistokes) in small amounts of polyalphaolefins; 400 selected from glycols, their monoesters and diesters A gasoline composition comprising a small amount of a polyoxyalkylene compound having a number average molecular weight ( _Mn ) in the range from 1 to 3000, wherein the weight ratio of polyalphaolefin: polyoxyalkylene compound is 1: A gasoline composition in the range of 10 to 10: 1. 2. The polyalphaolefin is from 8 to 1.
Composition according to claim 1, characterized in that it is derived from an alpha-olefinic monomer containing 2 carbon atoms. 3. The polyalpha-olefin is from 6 × 10 ⁻⁶ m ² / s to 1 × 10 ⁻⁵ m ² / s (6 at 100 ° C.).
Composition according to claim 1 or 2, characterized in that it has a viscosity in the range of centistokes to 10 centistokes. 4. The polyoxyalkylene compound has the general formula R ¹ —O— (R—O) _n —R ² (I) (wherein R ¹ and R ² are independently a hydrogen atom or C _1-40.
In which each R independently represents a C _2-8 alkylene group, and n represents a polyoxyalkylene compound having a M _{n in} the range of 700 to 2000). The composition according to any one of claims 1 to 3. 5. Composition according to claim 4, characterized in that R ¹ represents a C _8-20 alkyl group and R ² represents a hydrogen atom. 6. Composition according to claim 4 or 5, characterized in that each R independently represents a C _2-4 alkylene group. 7. The composition according to claim 1, wherein the polyalphaolefin and the polyoxyalkylene compound are present together in an amount in the range of 100 ppmw to 1200 ppmw, based on the total composition. 8. The composition according to claim 1, further comprising a small amount of at least one hydrocarbon-soluble ashless dispersant. 9. The dispersant has a polyolefin M _n of 80.
9. Composition according to claim 8, characterized in that it comprises a polyolefin-substituted succinimide derivative in the range 0 to 5000. 10. The ashless dispersant is 30 p based on the total composition.
10. Composition according to claim 8 or 9, characterized in that it is present in an amount ranging from pmw to 500 ppmw. 11. The composition according to claim 1, wherein the weight ratio of polyalphaolefin: polyoxyalkylene compound is in the range of 1: 5 to 5: 1. 12. A gasoline compatible diluent, a polyalphaolefin as defined in claim 1, a polyoxyalkylene compound as defined in claim 1 (polyalphaolefin:
The weight ratio of the polyoxyalkylene compound is 1:10 to 1
A concentrate suitable for addition to gasoline, characterized in that it is in the range of 0: 1) and at least one hydrocarbon-soluble ashless dispersant optionally added. 13. A polyalphaolefin and a polyoxyalkylene compound are present together in an amount ranging from 20% w to 80% w, and 5% w to 3 when an ashless dispersant is present.
13. Concentrate according to claim 12, characterized in that it is present in an amount in the range 0% w (all percentages are relative to the diluent). 14. A method for operating a spark ignition internal combustion engine, comprising introducing the gasoline composition according to any one of claims 1 to 11 into a combustion chamber of the engine. Method of operation.