JPH06200279A - Two stroke cycle engine lubricant consisting of vegetable oil and additive package - Google Patents

Abstract

This invention relates to a nitrogen-containing soluble organic composition comprising a combination of: (A) at least one natural oil comprising an animal oil or vegetable oil comprising a triglyceride of the formula <CHEM> wherein R<1>, R<2> and R<3> are independently saturated or unsaturated aliphatic hydrocarbyl groups containing from about 8 to about 24 carbon atoms and (B)(I) a detergent/dispersant comprising at least one acylated, nitrogen-containing compound having a substituent of at least 10 aliphatic carbon atoms made by reacting a carboxylic acylating agent with at least one amino compound containing at least one -NH group, said acylating agent being linked to said amino compound through an imido, amido, amidine, or acyloxy ammonium linkage. In another embodiment, the invention comprises a nitrogen-containing soluble organic composition comprising a combination of: (A) the natural oil as described above with (B) at least one detergent-dispersant selected from the group consisting of (I) the acylated, nitrogen-containing compound as described above, (II) at least one neutral or basic metal salt of an organic sulfur acid, phenol or carboxylic acid; (III) at least one hydrocarbyl-substituted amine wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 12 carbon atoms with the proviso that said amine is not the amino phenol (C); and (IV) at least one nitrogen-containing condensate of a phenol, aldehyde and amino compound having at least one -NH group; and (C) at least one amino phenol of the general formula <CHEM> wherein R<4> is a substantially saturated, hydrocarbon-based substituent of at least 10 aliphatic carbon atoms; a, b and c are each independently in integer of one up to three time the number of aromatic nuclei present in Ar with the proviso that the sum of a, b and c does not exceed the unsaturated valences of Ar; and Ar is an aromatic moiety having 0-3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, nitro, halo or combinations of two or more of said substituents.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to additive packages which are soluble in naturally occurring triglycerides to yield soluble organic compositions containing nitrogen. The composition thus obtained is useful in a two stroke cycle spark ignited internal combustion engine when blended with a fuel before or during use.

[0002]

BACKGROUND OF THE INVENTION Over the last several decades, the use of spark-ignited two-stroke cycle internal combustion engines (eg, Wankel type engines), including rotary engines, has been steadily increasing. These engines are now found in powered lawnmowers and other powered gardening equipment, powered chainsaws, pumps, generators, outboard engines for ships, snowmobiles, motorcycles, etc.

With the increasing use of two-stroke cycle engines, the need for oils to adequately lubricate such engines has been increased in connection with the increased severity of operating conditions. Problems associated with lubrication of two-stroke cycle engines include sticking of piston rings, rusting, poor lubrication of connecting rods and main bearings, and general formation of carbon and varnish deposits on engine internal surfaces. Burnish formation is a particularly troublesome problem because varnish buildup on the piston and cylinder walls will ultimately result in ring sticking which compromises the sealing function of the piston ring. This lack of hermeticity causes a loss of cylinder compression that is particularly damaging to the two-stroke cycle engine because the two-stroke cycle engine relies on suction to draw fresh fuel charge into the exhaust cylinder. therefore,
Ring sticking can result in poor engine performance and unnecessary consumption of fuel and / or lubricant. The problem of spark plug contamination and engine port blockage is also 2
It happens in the stroke cycle engine.

The unique problems and techniques associated with lubricating a two-stroke cycle engine are recognized by two-stroke cycle engine lubricant engineers as a different lubricant type. For example, U.S. Pat.
5; No. 3,004,837; and No. 3,753,905.

US Pat. No. 4,100,082 (Clason
n) et al., July 11, 1978) relates to additive formulations useful for oils of lubricating viscosity and normally liquid fuels. More specifically, this reference refers to aminophenols,
It relates to additive formulations with certain detergent / dispersants and to oils and fuels containing them which are particularly useful in two-stroke cycle engines.

US Pat. No. 4,663,063 (Davies
s), May 5, 1987) relates to additive formulations useful in lubricating compositions containing a major amount of oil of lubricating viscosity and a minor amount of additive formulation. This lubricant is useful in a two-stroke cycle internal combustion engine. More particularly, this reference relates to at least one alkylphenol having at least one hydrocarbon-based group having at least 10 aliphatic carbon atoms and at least one amino compound which is not an aminophenol. It relates to an additive composition containing a mixture. This reference also relates to a two-stroke cycle fuel-lubricant mixture, since two-stroke cycle engine oils are often compounded with fuel before or during use.

US Pat. No. 4,708,809 (Davies (Davi
s), 24 November 1987) relates to a lubricant composition containing a major amount of oil of lubricating viscosity and a minor amount of at least one alkylphenol. This lubricant is useful in a two-stroke cycle internal combustion engine. More specifically, this reference relates to such oils containing an alkylphenol having at least one hydrocarbon-based group having at least about 10 aliphatic carbon atoms. Since two-stroke cycle engine oils are often compounded with fuel before or during use, this reference also relates to two-stroke cycle fuel-lubricant mixtures.

[0008]

SUMMARY OF THE INVENTION The present invention includes a nitrogen-containing soluble organic composition having the following formulations (A) and (B): (A) an animal or vegetable oil containing a triglyceride of the formula: At least one natural oil:

[0009]

[Chemical 15]

Wherein R ¹ , R ² and R ³ are independently saturated or unsaturated aliphatic hydrocarbyl groups containing from about 8 to about 24 carbon atoms; and (B) (I) A detergent / dispersant containing at least one acylated nitrogen-containing compound having a substituent having at least 10 aliphatic carbon atoms, the compound comprising a carboxylic acylating agent and at least one Prepared by reacting with at least one amino compound containing a —NH group, the acylating agent is linked to the amino compound via an imidazoline imide bond, an amide bond, an amidine bond or an acyloxyammonium bond. ing.

In another embodiment, the present invention comprises the following:
(A), (B) and (C) containing a nitrogen-containing soluble organic composition having a combination of: (A) the above natural oil, (B) the following (I), (II), (III And at least one detergent / dispersant selected from the group consisting of (IV): (I) at least one of the above acylated nitrogen-containing compounds, (II) organic sulfur-containing acids, phenols or carboxylic acids A basic or basic metal salt; (III) at least one hydrocarbyl-substituted amine, wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 12 carbon atoms,
Provided that the amine is not an aminophenol (C); and (IV) at least one nitrogen-containing condensate of a phenol compound, an aldehyde compound and an amino compound having at least one -NH group; and (C) At least one aminophenol of the following general formula:

[0012]

[Chemical 16]

Where R ⁴ is a substantially saturated hydrocarbon-based substituent having at least 10 aliphatic carbon atoms; a, b and c are each independently an aromatic fragrance present in Ar. It is an integer from 1 to 3 times the number of nuclei, provided that the sum of a, b and c does not exceed the unsaturated valency of Ar; and Ar is lower alkyl, lower alkoxyl,
An aromatic moiety having 0 to 3 optional substituents selected from the group consisting of nitro, halo, or a combination of two or more of these substituents.

[0014]

According to the present invention, a nitrogen-containing soluble organic composition having the following composition (A) and (B) is obtained.

(A) at least one natural oil including animal or vegetable oils containing triglycerides of the formula:

[0016]

[Chemical 17]

Wherein R ¹ , R ² and R ³ are independently saturated or unsaturated aliphatic hydrocarbyl groups containing from about 8 to about 24 carbon atoms; and (B) (I) A detergent / dispersant containing at least one acylated nitrogen-containing compound having a substituent having at least 10 aliphatic carbon atoms, the compound comprising a carboxylic acylating agent and at least one Produced by reacting with at least one amino compound containing an —NH group, wherein the acylating agent is bonded to the amino compound via an imide bond, an amide bond, an amidine bond or an acyloxyammonium bond. There is.

[0018] In a preferred embodiment, the natural oil is a composition containing a vegetable oil.

In a further preferred embodiment, the vegetable oil is soybean oil, rapeseed oil, high oleic rapeseed oil, sunflower oil, high oleic acid sunflower oil, coconut oil, corn oil, peanut oil, sawarawa oil, palm. Oil, high oleic corn oil, palm kernel oil, meadow foam
A composition comprising wfoam oil, lesquerella oil and vernonia oil.

In a further preferred embodiment, the natural oil is a composition comprising animal oil including lard oil or tallow oil.

In a further preferred embodiment, the above R ¹ ,
R ² and R ³ are independently compositions containing about 12 to about 22 carbon atoms.

In a further preferred embodiment, the vegetable oil is a composition containing high oleic sunflower oil, high oleic safflower oil, high oleic corn oil or high oleic rapeseed oil.

In a further preferred embodiment, the detergent / dispersant (B) is at least one acylated nitrogen-containing compound having a substituent having at least 10 aliphatic carbon atoms, The compound comprises a carboxylic acylating agent,
It is produced by reacting with at least one amino compound containing at least one -NH group, and the acylating agent is a compound having an amino group through an imide bond, an amide bond, an amidine bond or an acyloxyammonium bond. The composition is combined with.

[0024] In a further preferred embodiment, the amino compound is a composition comprising an alkylene polyamine represented by the following general formula.

[0025]

[Chemical 18]

Wherein U is an alkylene group having 2 to 10 carbon atoms; each R ⁸ is independently a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group,
However, at least one R ⁸ is a hydrogen atom, and n is 1 to 10.

In a further preferred embodiment, the acylating agent contains a monocarboxylic or polycarboxylic acid or an equivalent reaction thereof, which contains an aliphatic hydrocarbyl substituent having at least about 30 carbon atoms. It is a composition of matter.

In a further preferred embodiment, the above substituents are compositions prepared from homopolymers or interpolymers of C _2-10 1-monoolefins or mixtures thereof.

In a further preferred embodiment, the homopolymer or interpolymer is a composition comprising a homopolymer or interpolymer of ethylene, propylene, 1-butene, 2-butene, isobutene or a mixture thereof. Is.

In a further preferred embodiment, the acylating agent is a composition consisting of at least one monocarboxylic acid having 12 to 30 carbon atoms or an equivalent reactant thereof. .

[0031] In a further preferred embodiment, the acylating agent is a composition comprising a mixture of fatty monocarboxylic acids or their equivalent reactants having straight or branched carbon chains. .

In a more preferred embodiment, the amino compound comprises an ethylene polyamine, propylene polyamine or trimethylene polyamine having at least 2 up to about 8 amino groups, or a mixture of such polyamines. It is a composition.

In a further preferred embodiment, the above
The composition has a weight ratio of (A) :( B) (I) in the range of about 97: 3 to about 80:20.

Further according to the present invention, a nitrogen-containing soluble organic composition having the following composition (A), (B) and (C) is obtained.

(A) At least one natural oil including animal or vegetable oils containing triglycerides of the formula:

[0036]

[Chemical 19]

Wherein R ¹ , R ² and R ³ are independently saturated or unsaturated, aliphatic hydrocarbyl groups containing from about 8 to about 24 carbon atoms; (B) ), (II), (III) and (IV) at least one detergent / dispersant selected from the group: (I) at least one with a substituent having at least 10 aliphatic carbon atoms An acylated nitrogen-containing compound according to claim 1, which is produced by reacting a carboxylic acid acylating agent with at least one amino compound containing at least one —NH group. Is
Bound to the amino compound via an imide bond, an amide bond, an amidine bond or an acyloxyammonium bond; (II) at least one neutral or basic metal salt of an organic sulfur-containing acid, phenol or carboxylic acid; (III) at least one hydrocarbyl-substituted amine, wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 12 carbon atoms,
Provided that the amine is not an aminophenol (C); and (IV) at least one nitrogen-containing condensate of a phenol compound, an aldehyde compound and an amino compound having at least one -NH group; and (C) At least one aminophenol of the following general formula:

[0038]

[Chemical 20]

Where R ⁴ is a substantially saturated hydrocarbon-based substituent having at least 10 aliphatic carbon atoms; a, b and c are each independently an aromatic fragrance present in Ar. It is an integer from 1 to 3 times the number of nuclei, provided that the sum of a, b and c does not exceed the unsaturated valency of Ar; and Ar is lower alkyl, lower alkoxyl,
An aromatic moiety having 0 to 3 optional substituents selected from the group consisting of nitro, halo, or a combination of two or more of these substituents.

[0040] In a preferred embodiment, the natural oil is a composition including a vegetable oil.

In a further preferred embodiment, the vegetable oil is soybean oil, rapeseed oil, high oleic rapeseed oil, sunflower oil, high oleic sunflower oil, coconut oil, peanut oil,
Sawarawa oil, high oleic safflower oil, palm oil,
Corn oil, high oleic corn oil, palm kernel oil, meadowfoam oil, les clera
A composition comprising querella oil and vernonia oil.

In a further preferred embodiment, the natural oil is a composition comprising animal oil including lard oil or tallow oil.

In a further preferred embodiment, the above R ¹ ,
R ² and R ³ are independently compositions containing about 12 to about 22 carbon atoms.

In a further preferred embodiment, the vegetable oil is a composition containing high oleic sunflower oil, high oleic safflower oil, high oleic corn oil or high oleic rapeseed oil.

In a further preferred embodiment, the above R
⁴ is a composition containing up to about 750 carbon atoms with no optional substituents attached to Ar.

In a further preferred embodiment, the above R
⁴ is a composition comprising an alkyl group or an alkenyl group.

In a further preferred embodiment, the above R
^4, contains about 30 to about 750 aliphatic carbon atoms, C ₂ -
A composition made from a homopolymer or interpolymer of C ₁₀ olefins.

In a further preferred embodiment, the olefin is a composition selected from the group consisting of ethylene, propylene, butylene and mixtures thereof.

In a further preferred embodiment, the above-mentioned a,
b and c are each 1, there are no optional substituents attached to Ar, and Ar consists of a benzene nucleus.

In a further preferred embodiment, the above R
⁴ is an alkyl or alkenyl group having at least 30 carbon atoms and up to about 750 carbon atoms, C ₂
Is a composition derived from a homopolymer or an interpolymer of C ₁₀ 1 -monoolefin.

In a further preferred embodiment, the aminophenol is a composition comprising an aminophenol of the formula:

[0052]

[Chemical 21]

Here, R ⁵ is about 30 to about 400 on average.
A substantially saturated hydrocarbon-based substituent having aliphatic carbon atoms, R ⁶ is lower alkyl, lower alkoxy,
An element selected from the group consisting of nitro and halo; and z is 0 or 1.

In a further preferred embodiment, the above R
⁵ is a pure hydrocarbyl aliphatic group having at least about 50 carbon atoms and is prepared from a polymer or interpolymer of olefins selected from the group consisting of C _2-10 1-monoolefins and mixtures thereof. It is a composition.

In a further preferred embodiment, the above z is 0.

In a further preferred embodiment, the detergent / dispersant is a composition comprising (II) at least one neutral or basic metal salt of an organic sulfur-containing acid, phenol or carboxylic acid. .

In a further preferred embodiment, the detergent / dispersant is a composition comprising at least one basic metal salt of an organic sulfonic acid or phenol.

In a further preferred embodiment, the metal is a composition comprising at least one alkali metal or alkaline earth metal.

In a further preferred embodiment, the detergent / dispersant is a composition comprising at least one alkaline earth metal sulfonate.

In a more preferred embodiment, the sulfonate is an alkyl-substituted benzene sulfonate, wherein the alkyl group is a composition having at least about 8 carbon atoms.

In a further preferred embodiment, the aminophenol is a composition comprising an aminophenol of the formula:

[0062]

[Chemical formula 22]

Here, R ⁵ is about 30 to about 400 on average.
A substantially saturated hydrocarbon-based substituent having aliphatic carbon atoms, R ⁶ is lower alkyl, lower alkoxy,
An element selected from the group consisting of nitro and halo; and z is 0 or 1. In a further preferred embodiment, the detergent / dispersant is a composition comprising (III) at least one hydrocarbyl-substituted amine.

In a further preferred embodiment, the amine is a composition consisting of a monoamine of the general formula AXNR ⁷ .

In a further preferred embodiment, the hydrocarbyl-substituted amine is a composition comprising a hydrocarbyl-substituted aminohydrocarbylmorpholine of the general formula:

[0066]

[Chemical formula 23]

Wherein R ⁷ is an aliphatic hydrocarbon group having about 30 to about 400 carbon atoms, A is hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or 1 to Ten
Is a hydroxyhydrocarbyl group having 3 carbon atoms and U is an alkylene group having 2 to 10 carbon atoms.

In a further preferred embodiment, the aminophenol is a composition comprising an aminophenol of the formula:

[0069]

[Chemical formula 24]

Here, R ⁹ is about 30 to about 400 on average.
A substantially saturated hydrocarbon-based substituent having aliphatic carbon atoms, R ⁶ is lower alkyl, lower alkoxy,
An element selected from the group consisting of nitro and halo; and z is 0 or 1.

In a further preferred embodiment, the detergent / dispersant is (I) at least one acylated nitrogen-containing compound having a substituent having at least 10 aliphatic carbon atoms. The compound is produced by reacting a carboxylic acid acylating agent with at least one amino compound containing at least one —NH group, and the acylating agent is an imide bond, an amide bond or an amidine bond. The composition is bound to the amino compound through a bond or an acyloxyammonium bond.

In a further preferred embodiment, the amino compound is a composition comprising an alkylene polyamine of the following general formula:

[0073]

[Chemical 25]

Wherein U is an alkylene group having 2 to 10 carbon atoms; each R ⁸ is independently a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group,
However, at least one R ⁸ is a hydrogen atom, and n is 1 to 10.

In a further preferred embodiment, the acylating agent is a monocarboxylic or polycarboxylic acid, or an equivalent thereof, containing an aliphatic hydrocarbyl substituent having at least about 30 carbon atoms. It is a composition comprising reactants.

In a further preferred embodiment, the above substituents are compositions prepared from homopolymers or interpolymers of C _2-10 1-monoolefins or mixtures thereof.

In a further preferred embodiment, the homopolymer or interpolymer comprises a homopolymer or interpolymer of ethylene, propylene, 1-butene, 2-butene, isobutene or a mixture thereof. Is.

In a further preferred embodiment, the aminophenol is a composition comprising an aminophenol of the formula:

[0079]

[Chemical formula 26]

Where R ⁵ is a substantially saturated hydrocarbon-based substitution having, on average, from about 30 to about 400 aliphatic carbon atoms located in the ortho or para positions of the hydroxyl group. The group R ^6, is an element selected from the group consisting of lower alkyl, lower alkoxy, nitro and halo; and z is 0 or 1.

In a further preferred embodiment, the acylating agent is a composition consisting of at least one monocarboxylic acid having 12 to 30 carbon atoms or an equivalent reactant thereof. .

In a further preferred embodiment, the acylating agent is a composition comprising a mixture of fatty monocarboxylic acids or their equivalent reactants having a straight or branched carbon chain. .

In a further preferred embodiment, the amino compound comprises ethylene polyamine, propylene polyamine or trimethylene polyamine having at least 2 up to about 8 amino groups, or a mixture of such polyamines. It is a composition.

In a further preferred embodiment, the aminophenol is a composition comprising an aminophenol of the formula:

[0085]

[Chemical 27]

Here, R ⁵ is about 30 to about 400 on average.
A substantially saturated hydrocarbon-based substituent having 4 aliphatic carbon atoms, R ⁶ is a member selected from the group consisting of lower alkyl, lower alkoxyl, nitro and halo; and z is 0 or 1 Is.

In a further preferred embodiment, the detergent / dispersant comprises (IV) a nitrogen-containing condensate of a phenol compound, an aldehyde compound and an amino compound having at least one --NH group. Is.

In a further preferred embodiment, the phenol is an alkyl-substituted phenol, the alkyl group being a composition having at least about 30 carbon atoms. In a more preferred embodiment, the aldehyde is a composition consisting of formaldehyde or an equivalent reactant thereof.

In a further preferred embodiment, the amino compound is a composition comprising an alkylene polyamine of the general formula:

[0090]

[Chemical 28]

Wherein U is an alkylene group having 2 to 10 carbon atoms; each R ⁸ is independently a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group,
However, at least one R ⁸ is a hydrogen atom, and n is 1 to 10.

In a further preferred embodiment, the condensate first reacts the phenol with the aldehyde in the presence of an alkali catalyst at temperatures up to 150 ° C,
Then, the intermediate reaction mixture thus formed is neutralized, and finally, the neutralized intermediate reaction mixture is reacted with at least one amino compound having at least one —NH group. The composition is

In a further preferred embodiment, the aminophenol is a composition comprising an aminophenol of the formula:

[0094]

[Chemical 29]

Here, R ⁵ is about 30 to about 400 on average.
A substantially saturated hydrocarbon-based substituent having 4 aliphatic carbon atoms, R ⁶ is a member selected from the group consisting of lower alkyl, lower alkoxyl, nitro and halo; and z is 0 or 1 Is.

In a further preferred embodiment, the aminophenol is a composition comprising an aminophenol of the formula:

[0097]

[Chemical 30]

Here, R ⁵ is about 30 to about 400 on average.
A substantially saturated hydrocarbon-based substituent having 4 aliphatic carbon atoms, R ⁶ is a member selected from the group consisting of lower alkyl, lower alkoxyl, nitro and halo; and z is 0 or 1 Is.

In a further preferred embodiment, about 70
~ 94 parts by weight (A), about 5-18 parts by weight (B) and about 1-12
It is a composition containing (C) in parts by weight.

Detailed Description of the Invention (A) Natural Oils In practicing the present invention, natural oils are used which are animal or vegetable oils of triglycerides of the formula:

[0101]

[Chemical 31]

In Structure (I), R ¹ , R ² and R ³ are independently hydrocarbyl groups containing from about 8 to about 24 carbon atoms. "Hydrocarbyl group" used here
The term represents a group having a carbon atom directly attached to the rest of the molecule. Within the context of the present invention, the hydrocarbyl group has predominantly aliphatic hydrocarbon character. Such aliphatic hydrocarbon groups include: (1) aliphatic hydrocarbon groups; that is, alkyl groups (eg, heptyl, nonyl, undecyl, tridecyl, heptadecyl); a single double bond Containing alkenyl groups (eg heptenyl, nonenyl, undecenyl, tridecenyl, heptadecenyl, heneicosenyl); alkenyl groups containing two or three double bonds (eg 8,11-heptadecadienyl and 8,11, 14-Heptadecatrienyl). Including all of these isomers,
Straight-chain groups are preferred.

(2) Substituted aliphatic hydrocarbon groups; that is, groups containing non-hydrocarbon substituents which, within the context of this invention, do not predominantly alter the hydrocarbon character of the group. . Suitable substituents are known to those skilled in the art; examples include hydroxy, carboalkoxy (especially lower carboalkoxy) and alkoxy (especially lower alkoxy), the term "lower" being 7 It represents a group containing the following carbon atoms.

(3) a hetero group; that is, within the context of this invention, that is, while having predominantly aliphatic hydrocarbon character, having atoms other than carbon present in the chain or ring, but otherwise aliphatic. A group composed of carbon atoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, oxygen and sulfur.

The hydrocarbyl group can be saturated or unsaturated or a mixture of both. Preferred triglycerides have from about 8 aliphatic groups represented by R ¹ , R ² and R ^3.
Those having about 24, preferably 12 to 22 carbon atoms. Typical triglycerides used in the present invention include coconut oil, safflower oil, high oleic acid safflower oil, sunflower oil, rapeseed oil (both high and low erucic acid content), high Oleic rapeseed oil, high oleic sunflower oil, cottonseed oil, peanut oil, corn oil, high oleic corn oil, castor oil,
Meadowfoam oil, lesquerel
la) oil, soybean oil, palm oil, palm kernel oil, sesame oil, vernonia oil and animal fats and oils having a given structural formula (I) (eg lard oil and beef tallow). The triglyceride is preferably a vegetable oil.

Naturally occurring triglycerides are not chemically pure. That is, soybean oil meets the parameters of structure (I), where R ¹ , R ² and R ³ contain about 8 to 24 carbon atoms, while soybean oil is within the triglyceride structure. Containing a mixture of fatty acids of different carbon lengths. Table 1 outlines the composition of a few natural oils that are triglycerides.

[0107]

[Table 1]

Preferred vegetable oils of the invention are defined as high oleic sunflower oil, high oleic rapeseed oil (high oleic acid is defined as having an oleic acid content of at least 70%, preferably at least 80%. , Sunflower (Helianthus sp.), From SVO Enterprises (East Lake, Ohio),
Sunyl ^R 70 or Sunnyl ^R 80, available as high oleic sunflower oil), high oleic corn oil, soybean oil, castor oil and vernonia
There is oil. Vernonia oil is preferred because it is a naturally occurring epoxidized oil.

[0109]

[Chemical 32]

However, it is also within the scope of this invention to synthetically epoxidize naturally occurring oils that are not naturally epoxidized. That is, natural oils may be reacted with aqueous peracetic acid or with hydrogen peroxide and acetic acid in a manner well known to those skilled in the art. The epoxide content of this synthetic epoxidized natural oil varies with the degree of completion of the epoxidation reaction and the amount of unsaturation present in the triglyceride of the natural oil. Characteristically, such epoxidized oils have an oxirane oxygen content of at least 3%, preferably 5-15%. One example of epoxidized natural oil is epoxidized soybean oil, and one of the epoxidized soybean oils is a compound of the formula:

[0111]

[Chemical 33]

(B) Detergent / Dispersant In one embodiment, the detergent / dispersant is (B) (I), which is combined with (A). In another embodiment, this cleaning /
The dispersant is selected from the group consisting of compounds (B) (I) to (B) (IV), which is combined with (A) and (C).

Detergents / Dispersants Generally Used in the Invention
(B) is a substance known to those skilled in the art and is described in many books, papers and patents. Many of these are discussed below in connection with specific types of detergent / dispersants, in which case their disclosure is discussed in the patent specification pointing to these detergents / dispersants. It can be understood that what is shown here is related to the task.

(B) (I) Acylated Nitrogen-Containing Compound Many of which are produced by reacting a carboxylic acylating agent with an amino compound having a substituent R ⁹ having at least 10 aliphatic carbon atoms. The acylated nitrogen-containing compounds of are well known to those skilled in the art. In such compositions, the acylating agent comprises an imidazoline imide bond, an amide bond,
It is linked to the amino compound via an amidine bond or an acyloxyammonium bond. The moiety derived from the carboxylic acylating agent of this molecule, or the moiety derived from the amino compound of this molecule has a substituent with 10 aliphatic carbon atoms, preferably 30 aliphatic carbon atoms. You can However, preferably this substituent is on the acylating agent moiety. This acylating agent can be prepared from formic acid and its acylated derivatives to produce 5,000, 10,000 or 20,00
Acylating agents with high molecular weight aliphatic substituents having up to 0 carbon atoms can be varied. This amino compound is
It can vary from ammonia itself to amines with aliphatic substituents having up to about 30 carbon atoms. A more detailed discussion of R ⁹ can be found herein below.

Typical classes of acylated amino compounds useful in making the compositions of the present invention include at least 10
Some are prepared by reacting an acylating agent having an aliphatic substituent with 4 carbon atoms with a nitrogen compound characterized by the presence of at least one -NH group. Typically the acylating agent is a monocarboxylic acid or polycarboxylic acid (or their reactive equivalents), for example a substituted succinic acid or propionic acid, the amino compound being a polyamine or polyamine mixture, Most typically it is a mixture of ethylene polyamines. The aliphatic substituent R ^{9 in} such an acylating agent is
Often, it has at least about 50 and up to about 400 carbon atoms. The aliphatic substituent R ⁹ is derived from homopolymerized or interpolymerized C _2-10 1-olefins or a mixture of both. Usually R ⁹ is derived from ethylene, propylene, butylene and mixtures thereof. Typically this substituent is derived from the polymeric isobutene. Examples of amino compounds useful in making these acylated compounds include: (1) polyalkylene polyamines of the general formula:

[0116]

[Chemical 34]

Here, each R ⁸ is independently a hydrogen atom, a lower alkyl group, a lower hydroxyalkyl group or C _1-12.
Hydrocarbon-based groups, provided that at least one
R ⁸ is a hydrogen atom, n is an integer of 1 to 10, and U is a C _2-10 alkylene group; (2) Heterocycle-substituted polyamine of the formula:

[0118]

[Chemical 35]

Where R ⁸ and U are the same as previously defined, m is 0 or an integer from 1 to 10 and m ′ is 1
An integer of ˜10 and Y is an oxygen atom or a divalent sulfur atom or a N—R ⁸ group; and (3) an aromatic polyamine of the general formula: Ar (NR ⁸ ₂ ) _y Formula V where in, Ar is an aromatic nucleus, each R ⁸ having from 6 to about 20 carbon atoms are the same as those of the previously defined and y is from 2 to about 8. This polyalkylene polyamine
Specific examples of (1) include ethylenediamine, tetra (ethylene) pentamine, tri (trimethylene) tetramine,
1,2-propylenediamine and the like. Specific examples of this heterocycle-substituted polyamine (2) include N-2-aminoethylpiperazine, N-2 and N-3 aminopropylmorpholine, N-3-
(Dimethylamino) propyl piperazine and the like. Specific examples of this aromatic polyamine (3) include various isomeric phenylenediamines, various isomeric naphthalenediamines, and the like.

Useful acylated nitrogen compounds have been described in a number of patents, including US Pat. No. 3,172,892.
No .; 3,219,666; 3,272,746; 3,310,492;
No. 3,341,542; No. 3,444,170; No. 3,455,831; No. 3,4
No. 55,832; No. 3,576,743; No. 3,630,904; No. 3,632,51
No. 1; and No. 3,804,763. Typical acylated nitrogen-containing compounds of this class include poly (isobutene) -substituted succinic anhydride acylating agents (eg, anhydrides,
Acids, esters, etc., wherein the poly (isobutene) substituent has between about 50 and about 400 carbon atoms)
And an ethylene polyamine mixture having from 3 to about 7 amino nitrogen atoms per ethylene polyamine and having from about 1 to about 6 ethylene units, which is prepared by condensation of ammonia with ethylene chloride. ) Is produced by reacting with. Given the wide disclosure of this type of acylated amino compound, its nature and method of preparation need not be discussed further here. Rather, the content of the above-referenced U.S. patents is set forth herein for disclosure of acylated amino compounds and methods of making them.

Other types of acylated nitrogen compounds belonging to this class react the above alkyleneamines with the abovementioned substituted succinic acids or their anhydrides and aliphatic monocarboxylic acids having from 2 to about 22 carbon atoms. By doing so, it is manufactured. For these types of acylated nitrogen compounds, the molar ratio of succinic acid to monocarboxylic acid ranges from about 1: 0.1 to about 1: 1. Typical monocarboxylic acids include formic acid, acetic acid, dodecanoic acid, butanoic acid, oleic acid, stearic acid, a commercial mixture of stearic acid isomers known as isostearic acid, and triacrylic acid. Such materials are described in U.S. Pat.
936 and 3,250,715 are more fully described, the contents of which are provided herein in this regard.

Yet another type of acylated nitrogen compound useful in making the compositions of the present invention is a fatty monocarboxylic acid having from about 12 to 30 carbon atoms and an alkylene amine (typically Are reaction products with ethylene polyamines, propylene polyamines or trimethylene polyamines containing 2 to 8 amino groups and mixtures thereof). This fatty monocarboxylic acid is generally
It is a mixture of straight and branched chain fatty carboxylic acids containing 12 to 30 carbon atoms. A widely used type of acylated nitrogen compound is the above alkylene polyamine and 5
Is prepared by reacting with a fatty acid mixture having from about 30 mole percent straight chain fatty acids and from about 70 to about 95 mole percent branched chain fatty acids. Some commercially available mixtures are widely known as isostearic acid. These mixtures are produced as by-products from the dimerization of unsaturated fatty acids described in US Pat. Nos. 2,812,342 and 3,260,671.

Branched chain fatty acids may also include those in which the branch is not alkyl in nature, such as phenylstearic acid and cyclohexylstearic acid and chlorostearic acid. Branched chain fatty carboxylic acid / alkylene polyamine products have been extensively described in the art. For example, U.S. Pat. No. 3,110,673; 3,251,853
No .; 3,326,801; 3,337,459; 3,405,064;
See, 3,429,674; 3,468,639; 3,857,791. The content of these patents is set forth herein with respect to the disclosure of fatty acid / polyamine condensates and their use in lubricating oil formulations.

(B) (II) Organic sulfur-containing acid, carboxylic acid or
Neutral or Basic Metal Salts of Phenol or Phenol The choice of metal used to make these salts is generally not critical, and thus virtually any metal can be used. Certain metals are more commonly used for reasons of utility, cost and maximum efficiency. These include alkali metals and alkaline earth metals (ie, Group IA and Group IIA metals excluding francium and radium). Group IIB metals and polyvalent metals such as aluminum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel and copper can also be used. Salts containing mixtures of two or more ions of these metals are often used.

These salts can be neutral or basic. The former contains just enough metal cations to neutralize the acid groups present in the salt anions; the latter contains excess metal cations, often overbased, hyperbased salts. Also called super-based salt.

These basic salts and neutral salts include oil-soluble organic sulfur-containing acids (for example, sulfonic acid, sulfamic acid, thiosulfonic acid, sulfinic acid, sulfenic acid,
Partially esterified sulfuric acid, sulfurous acid and thiosulfuric acid). Generally, these salts are salts of carbocyclic sulfonic acids or aliphatic sulfonic acids.

Carbocyclic sulfonic acids include mononuclear or polynuclear aromatic compounds or cycloaliphatic compounds. These oil-soluble sulfonates are often
It can be represented by the formula: [R _x T− (SO ₃ ) _y ] _z M _b Formula VI [R ¹⁰ − (SO ₃ ) _a ] _d M _b Formula VII In the above formula, M is Is any of the described metal cations or hydrogen; T is a cyclic nucleus, such as benzene, naphthalene, anthracene, phenanthrene, diphenylene oxide, thianthrene, phenothioxine,
Diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine,
Cyclohexane, petroleum naphthene, decahydronaphthalene, cyclopentane, etc .; R _{x in} Formula VI is an aliphatic group (eg, alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxyalkyl, etc.); x is at least 1; and R _x + T is at least about 1 in total
Contains 5 carbon atoms. R ^{10 in} formula VII is an aliphatic group containing at least about 15 carbon atoms, and
M is either a metal cation or hydrogen. Examples of types of R ¹⁰ groups include alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl and the like. R ¹⁰
Specific examples of petrolatum, saturated and unsaturated paraffin waxes, and polyolefins (which include about
There are 15 ～7000 or more groups olefin derived from encompassed) such as _{C 2, C 3, C 4} , C 5, C 6 to polymerized containing carbon atoms. The T, R and R ¹⁰ groups of the above formula also include, in addition to those enumerated above, other inorganic or organic substituents such as hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide, disulfide. Can be included. In Formula VI, x, y, z and b are at least 1, and similarly in Formula VII, a,
b and d are at least 1.

The following are specific examples of oil-soluble sulfonic acids that fall within the scope of Formulas VI and VII above, and such examples also illustrate salts of sulfonic acids useful in the present invention. It should be understood to be useful. In other words, for any sulfonic acid listed, their corresponding neutral and basic metal salts are also intended to be illustrative. Such sulfonic acids include mahogany sulfonic acid; brightstock sulfonic acid; 100
Sulfonic acids derived from lubricating oil fractions having a Saybolt viscosity of about 100 seconds at 210 ° F to about 200 seconds at 210 ° F; petrolatum sulfonic acid; for example, benzene, naphthalene, phenol, diphenyl ether, naphthalenedisulfide, diphenylamine, thiophene, α Mono- and polywax-substituted sulphonic acids and polysulphonic acids such as chloronaphthalene; other substituted sulphonic acids (eg alkylbenzene sulphonic acids where the alkyl group has at least 8 carbons), cetyl Phenol monosulfide sulfonic acid, dicetyl cyananthrene disulfonic acid, dilauryl-β-naphthyl sulfonic acid,
There are dicapryl nitronaphthalene sulfonic acids, and alkaryl sulfonic acids (eg, dodecylbenzene "bottoms" sulfonic acid).

The latter was derived from benzene alkylated with propylene tetramer or isobutene trimer to introduce one, two, three or more branched C ₁₂ substituents on the benzene ring. It is an acid. Dodecylbenzene bottoms, primarily mixtures of monododecylbenzene and didodecylbenzene, are available as by-products of the manufacture of household detergents. Similar products obtained from alkylated bottoms formed during the production of linear alkyl sulfonates (LAS) are also useful in making the sulfonates used in this invention.

It is well known to the person skilled in the art to produce sulphonates from by-products of detergent production, for example by reaction with SO ₃ . For example, John Willey and Sons (Jo
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, 19 published by hn Wiley & Sons (New York (1969)).
Vol., P. 291 and subsequent chapters "Sulfonates". Other descriptions of neutral and basic sulfonates, and methods of making them, can be found in the following US patents: US Pat. Nos. 2,174,110; 2,174,506; 2,174,508;
No. 2,193,824; No. 2,197,800; No. 2,202,781; No. 2,2
No. 12,786; No. 2,213,360; No. 2,228,598; No. 2,233,67
No. 6; No. 2,239,974; No. 2,263,312; No. 2,276,090;
No. 2,276,097; No. 2,315,514; No. 2,319,121; No. 2,3
No. 21,022; No. 2,333,568; No. 2,333,788; No. 2,335,25
No. 9; No. 2,337,552; No. 2,346,568; No. 2,366,027;
No. 2,374,193; No. 2,383,319; No. 3,312,618; No. 3,4
71,403; 3,488,284; 3,595,790 and 3,79
No. 8,012. These contents are presented here for disclosure in this regard.

Aliphatic sulfonic acids (eg paraffin wax sulfonic acid, unsaturated paraffin wax sulfonic acid, hydroxy-substituted paraffin wax sulfonic acid, hexapropylene sulfonic acid, tetraamylene sulfonic acid, polyisobutene sulfonic acid (wherein Polyisobutene contains from 20 to 7,000 or more carbon atoms), chlorine-substituted paraffin wax sulfonic acid, nitroparaffin wax sulfonic acid, etc.);
Also included are cycloaliphatic sulfonic acids (eg, petroleum naphthene sulfonic acid, cetyl cyclopentyl sulfonic acid, lauryl cyclohexyl sulfonic acid, bis- (diisobutyl) cyclohexyl sulfonic acid, etc.), mono- or polywax substituted cyclohexyl sulfonic acids, and the like.

With respect to the sulfonic acids or salts thereof described herein and in the appended claims, the term "petroleum sulfonic acid" or "petroleum sulfonate" refers to all sulfonic acids derived from petroleum products or their salts. It is intended herein to be used to include salt. A particularly useful group of petroleum sulphonic acids is the mahogany sulphonic acid, which is obtained as a by-product from the production of petroleum white oil by the sulfuric acid process (so called because it has a reddish brown color).

In general, the Group IA, Group IIA and Group IIB neutral and basic salts of the synthetic sulfonic and petroleum sulfonic acids described above are useful in the practice of this invention.

Carboxylic acids for which suitable neutral and basic salts may be prepared for use in the invention include aliphatic,
Cycloaliphatic and aromatic mono- and polybasic carboxylic acids such as naphthenic acid, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids, and alkyl- or alkenyl-substituted fragrances. Group carboxylic acids). These aliphatic acids generally contain at least 8 carbon atoms, preferably at least 12 carbon atoms. Usually, they do not have more than about 400 carbon atoms. Generally, if the aliphatic carbon chain is branched, these acids will be more oil soluble for a given carbon atom content. These cycloaliphatic carboxylic acids and aliphatic carboxylic acids can be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, α-linolenic acid, propylene tetramer-substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid,
Lauric acid, oleic acid, lysine (ricinlic) acid, undecyl acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalenecarboxylic acid,
Stearyl octahydroindene carboxylic acids, palmitic acid, commercially available mixtures of two or more carboxylic acids (eg tall oil acid, rosin acid) and the like.

A preferred group of oil-soluble carboxylic acids useful in preparing the salts used in this invention are oil-soluble aromatic carboxylic acids. These acids are represented by the general formula:

[0136]

[Chemical 36]

Where R ¹¹ is an aliphatic hydrocarbon-based group having at least 4 carbon atoms and up to about 400 aliphatic carbon atoms, a is an integer from 1 to 4, Ar ^* is about 14
Polyvalent aromatic hydrocarbon nuclei having up to 4 carbon atoms, each X
Are independently sulfur or oxygen atoms, and m is an integer from 1 to 4; provided that R ¹¹ and a are averaged by the R ¹¹ group for each acid molecule represented by formula VIII. Such that at least 8 aliphatic carbon atoms are obtained. Examples of aromatic nuclei represented by various Ar ^* are polyvalent aromatic groups derived from benzene, naphthalene, anthracene, phenanthrene, indene, fluorene, biphenyl and the like. Generally, the group represented by Ar ^* is benzene or naphthalene (eg, phenylene and naphthylene, such as methylphenylene, ethoxyphenylene, nitrophenylene, isopropylphenylene, hydroxyphenylene, mercaptophenylene, N, N-diethylaminophenylene, chlorophenylene. , Dipropoxynaphthylene, triethylnaphthylene, and their similar trivalent, tetravalent, pentavalent nuclei).

The R ¹¹ group is usually a pure hydrocarbyl group, preferably a group such as an alkyl or alkenyl group. However, this R ¹¹ group is, for example,
It may contain a small number of substituents such as: phenyl, cycloalkyl (eg cyclohexyl, cyclopentyl etc.) and non-hydrocarbon groups (eg nitro, amino, halo (eg chloro, bromo etc.)), lower alkoxy. Substituent, lower alkyl mercapto substituent, oxo substituent (ie, ═O), thio group (ie, ═S),
Interrupting groups (e.g., -NH-, -O-, -S-), etc.
The substantially hydrocarbon character of this R ¹¹ group is retained.
The hydrocarbon nature, any non-carbon atoms present in R ¹¹ group, unless it is clear that more than about 10% of the total weight of the R ¹¹ group, for purposes of the present invention is held .
Examples of R ¹¹ groups include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, docosyl, tetracontyl,
5-chlorohexyl, 4-ethoxypentyl, 4-hexenyl, 3-cyclohexyloctyl, 4- (p-chlorophenyl) octyl, 2,3,5-trimethylheptyl, 4-ethyl-5
-Methyloctyl, and substituents derived from polymerized olefins are included: polychloroprene, polyethylene, polypropylene, polyisobutylene, ethylene-propylene copolymers, chlorinated olefin polymers, oxidized ethylene-. Propylene copolymer etc. Similarly, the Ar ^* group may contain non-hydrocarbon substituents, for example various substituents such as: lower alkoxy groups, lower alkylmercapto groups, nitro groups, halo groups, less than 4 carbons. Alkyl or alkenyl groups having atoms, hydroxy, mercapto and the like.

One group of particularly useful carboxylic acids is of the formula:

[0140]

[Chemical 37]

Here, R ¹¹ , X, Ar ^* , m and a are represented by the formula V
As defined in III and p is an integer from 1 to 4, usually 1 or 2. Of this group, a particularly preferred class of oil-soluble carboxylic acids is of the formula:

[0142]

[Chemical 38]

Wherein R ¹² of the formula X is at least 4
An aliphatic hydrocarbon group containing about 400 carbon atoms, a is an integer from 1 to 3, b is 1 or 2, c is 0, 1 or 2,
And preferably 1, provided that R ¹² and a are
Is a value such that this acid molecule contains, on average, about 12 aliphatic carbon atoms in the aliphatic hydrocarbon substituent per acid molecule. In the latter group of oil-soluble carboxylic acids,
Aliphatic hydrocarbon substituted salicylic acid, wherein each aliphatic hydrocarbon substituent contains an average of at least about 16 carbon atoms per substituent and 1 to 3 substituents per molecule. Those containing are particularly useful. In salts prepared from such salicylic acids, the aliphatic hydrocarbon substituents are polymerized olefins, especially polymerized lower 1-monoolefins (eg polyethylene, polypropylene,
Those derived from polyisobutylene, ethylene / propylene copolymers, etc.) and having an average carbon content of from about 30 to about 400 carbon atoms are particularly useful.

The carboxylic acids corresponding to formulas VIII-IX above are:
It is well known or can be prepared according to methods well known in the art. Methods of preparing carboxylic acids of the types exemplified in the above formulas, and their neutral and basic metal salts are well known and are disclosed, for example, in the following US patents: US Patent No. 2,197,832; No. 2,197,835; No.
No. 2,252,662; No. 2,252,664; No. 2,714,092; No. 3,41
0,798; and 3,595,791.

Other types of neutral and basic carboxylates for use in the present invention include those derived from alkenyl succinates of the general formula:

[0146]

[Chemical Formula 39]

Where R ¹¹ is as defined above in formula VIII. Such salts and methods for their preparation are described in US Pat. Nos. 3,271,130; 3,567,637 and 3,
No. 632,510, the content of which is
Shown here.

Other patents which specifically describe the process for preparing the basic salts of the sulfonic acids, carboxylic acids and mixtures of two or more thereof include the following US patents: US Pat. No. 2,501,731 No. 2,616,904 No. 2,
No. 616,905; No. 2,616,906; No. 2,616,911; No. 2,616,9
No. 24; No. 2,616,925; No. 2,617,049; No. 2,777,874
No. 3,027,325; 3,256,186; 3,282,835;
No. 3,384,585; No. 3,373,108; No. 3,365,396; No. 3,3
No. 42,733; No. 3,320,162; No. 3,312,618; No. 3,318,80
No. 9; No. 3,471,403; No. 3,488,284; No. 3,595,790;
And No. 3,629,109. The disclosures of these patents are set forth herein for disclosure of certain suitable basic metal salts, as well as for disclosure in this regard: neutral and basic salts of phenols (generally , Known as phenates) are also useful in the compositions of the present invention and are well known to those skilled in the art. The phenols from which these phenates are formed are of the general _{^{formula: (R 11) n (Ar}} *) - (XH) m Formula XII ^{wherein, R 11, n, Ar *} , X and m Has the same meaning as above and has the selectivity as described above for formula VIII. The same examples as described for formula VIII also apply.

Some commonly available classes of phenates are those made from phenols of the general formula:

[0150]

[Chemical 40]

Here, a is an integer of 1 to 3, b is 1 or 2, z is 0 or 1, and R ¹³ of the formula XIII is 30 or more on average.
A substantially saturated hydrocarbon-based substituent having about 400 aliphatic carbon atoms, and R ¹⁴ is a lower alkyl group,
It is selected from the group consisting of lower alkoxyl groups, nitro groups, and halo groups.

For use in the present invention, certain classes of phenates may be provided with a phenol as described above and a sulfurizing agent (eg,
There are sulfurized phenates of basic (ie, overbased, etc.) Group IIA metals prepared by sulfurization with sulfur, sulfur halides or sulfides or hydrogen sulfides. Methods for producing these sulfurized phenates are described in US Pat. Nos. 2,680,096; 3,036,971 and 3,
No. 775,321, the contents of which are set forth herein for disclosure in this regard.

Other useful phenates are those made from phenols linked by alkylene (eg methylene) bridges. These are typically prepared by reacting a single or multiple ring phenol with an aldehyde or ketone in the presence of an acid or base catalyst. Such bound phenates as well as sulfurized phenates are described in detail in U.S. Pat. No. 3,350,038, particularly columns 6-8, the contents of which are provided herein for disclosure in this regard.

Of course, mixtures of two or more of the organic sulfur-containing acids, carboxylic acids and phenol neutral and basic salts described above can be used in the compositions of this invention. Typically the neutral and basic salts are sodium, lithium, magnesium, calcium or barium salts, including mixtures of any two or more of these.

(B) (III) Hydrocarbyl Substituted Amine Hydrocarbyl substituted amines used in making the compositions of the present invention are well known to those skilled in the art and have been described in a number of patents. These include US Pat. No. 3,275,554;
No. 3,438,757; No. 3,454,555; No. 3,565,804; No. 3,7
55,433; and 3,822,209. The content of these patents is provided herein for the disclosure of suitable hydrocarbyl amines for use in the present invention, including methods for their preparation.

Hydrocarbyl amines useful in the present invention include monoamines of the general formula: AXNR ⁷ Formula XIV Examples of such monoamines include: poly (propylene) amine N, N-dimethyl. -N-poly (ethylene / propylene) amine (50:50 molar ratio monomer) poly (isobutene) amine N, N-di (hydroxyethyl) -N-poly (isobutene) amine poly (isobutene / 1-butene / 2-Butene) amine (50:25:25 molar ratio monomer) N- (2-hydroxypropyl) -N-poly (isobutene) amine N-poly (1-butene) aniline N-poly (isobutene) morpholine Hydrocarbyl-substituted amines useful in forming the compositions of the invention include certain N-aminohydrocarbylmorpholines, not covered by general formula XIV above. These hydrocarbyl substituted aminohydrocarbyl morpholines have the following general formula:

[0157]

[Chemical 41]

Wherein R ⁷ is an aliphatic hydrocarbon group having about 30 to about 400 carbon atoms, A is hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or 1 to Ten
Is a hydroxyhydrocarbyl group having 3 carbon atoms and U is an alkylene group having 2 to 10 carbon atoms. These hydrocarbyl substituted aminohydrocarbyl morpholines and polyamines described in Formula XV are among the typical hydrocarbyl substituted amines used in preparing the compositions of the present invention.

(B) (IV) Phenol, aldehyde and
Nitrogen-containing Condensates of Mino Compounds Phenol / aldehyde / amino compounds useful in making the compositions of the present invention include those commonly referred to as Mannich condensation products. Generally, these are at least one active hydrogen compound having at least one hydrogen atom bound to an aromatic carbon atom (eg, a hydrocarbon-substituted phenol (eg, an alkyl group of at least about 30).
Alkylphenols having from 1 to about 400 carbon atoms)) and at least one aldehyde or aldehyde-producing material (typically formaldehyde or formaldehyde precursor) and at least one NH group having at least one NH group. It is produced by reacting with an amino compound or a polyamino compound simultaneously or successively. These amino compounds have 1 to 30
Hydrocarbon substituents having 1 carbon atom or 1 to about 30
Mention may be made of primary or secondary monoamines having hydroxy-substituted hydrocarbon substituents having 4 carbon atoms.
Other types of representative amino compounds include the polyamines described in the discussion of acylated nitrogen-containing compounds.

Illustrative monoamines include methylethylamine, methyloctadecylamine, aniline, diethylamine, diethanolamine, dipropylamine and the like. U.S. patents below, includes a broad description of the Mannich condensation product may be used in preparing the compositions of the present invention: U.S. Patent 2,459,112 3,413,347 3,558,743 2,962,442 3,442,808 3,586,629 2,984,550 3,448,047 3,591,598 3,036,003 3,454,497 3,600,372 3,166,516 3,459,661 3,634,515 3,236,770 3,461,172 3,649,229 3,355,270 3,493,520 3,697,574 3,368,972 3,539,633 The content of these patents is set forth herein for disclosure regarding the manufacture and use of Mannich condensation products in lubricant compositions.

Condensates made from sulfur-containing reactants can also be used in the compositions of this invention. Such sulfur-containing condensates are described in US Pat. Nos. 3,368,972; 3,649,2
No. 29; No. 3,600,372; No. 3,649,659; and No. 3,741,
It is described in No. 896. The contents of these patents are provided herein for the disclosure of sulfur-containing Mannich condensation products. Generally, the condensates used in making the compositions of the present invention will have alkyl substituents having from about 6 to about 400 carbon atoms, more typically from 30 to about 250 carbon atoms. Manufactured from the phenols that they have. These typical condensates are prepared from formaldehyde or C _2-7 aliphatic aldehydes and amino compounds such as those used in preparing the acylated nitrogen-containing compounds described in (B) (I). To be done.

These preferred condensates contain 1 part by mole of the phenolic compound, about 1 to about 2 parts by mole of the aldehyde and about 1 to about 5 equivalents of the amino compound (equivalent of the amino compound is present in its molecular weight). Is divided by the number of NH groups). The conditions under which such condensation reactions occur are well known to those skilled in the art, as evidenced by the above patents. Accordingly, the content of these patents is also set forth herein for disclosure regarding reaction conditions.

A particularly preferred class of condensation products for use in the present invention is prepared by the "two-step process" disclosed in US Patent Application No. 451,644, filed March 15, 1974 and commonly assigned. There is something. In summary, these nitrogen-containing condensates include (1) alkaline reagents (e.g.,
Containing an aliphatic or cycloaliphatic-based substituent having at least about 30 carbon atoms and up to about 400 carbon atoms at a temperature of up to about 150 ° C. in the presence of an alkali metal hydroxide). Reacting at least one hydroxyaromatic compound with a lower aliphatic C _1-7 aldehyde or a reversible polymer thereof; (2) substantially neutralizing the intermediate reaction mixture thus formed. That; and
(3) It is produced by reacting this neutralized intermediate with at least one compound containing an amino group having at least one —NH group.

More preferably, these two-stage condensates are (a) phenol with a hydrocarbon-based substituent having from about 30 to about 250 carbon atoms, which substituent is propylene, 1- Butene, 2-butene or isobutene polymers) and (b) formaldehyde or reversible polymers thereof (eg trioxane, paraformaldehyde) or their functional equivalents (eg
Methylal), and (c) an alkylene polyamine having between 2 and 10 nitrogen atoms (eg, ethylene polyamine). A more detailed description of this preferred class of condensates can be found in U.S. Patent Application No.
No. 451,644, the contents of which are provided here for disclosure regarding two-stage condensates.

(C) Aminophenol The aromatic moiety Ar of formula I is a single aromatic nucleus (eg, benzene nucleus, pyridine nucleus, thiophene nucleus, 1,2,3,4-tetrahydronaphthalene nucleus, etc.), or polynuclear It can be an aromatic moiety. Such polynuclear moieties can be of the fused type; that is, where at least one aromatic nucleus is fused at two points with another nucleus, for example, they are naphthalene,
Found in anthracene, azanaphthalene, etc. On the other hand, such polynuclear aromatic moieties may be of the bond type in which at least two nuclei (either mononuclear or polynuclear) are linked to each other via cross-links. Such crosslinks may be selected from the group consisting of: carbon-carbon single bond, ether bond, keto bond, sulfide bond,
A polysulfide bond having 2 to 6 sulfur atoms,
Sulfinyl bond, sulfonyl bond, methylene bond, alkylene bond, di (lower alkyl) methylene bond, lower alkylene ether bond, alkylene keto bond, lower alkylene sulfur bond, lower alkylene polysulfide bond having 2 to 6 carbon atoms, amino Bonds, polyamino bonds, and mixtures of such divalent crosslinks. In some cases, there may be more than one crosslink between aromatic nuclei in Ar. For example, a fluorene nucleus has two benzene nuclei attached to both a methylene bond and a covalent bond. Such nuclei are considered to have three nuclei, but only two of them are aromatic. However, usually Ar will have only carbon atoms present in the aromatic nucleus itself (plus the lower alkyl or alkoxy substituents present).

The number of aromatic nuclei in Ar, whether of single type, condensed type or bonded type, plays a role in determining the integer values of a, b and c in formula II. For example, Ar
When A contains a single aromatic nucleus, a, b and c are each independently 1-4. When Ar contains two aromatic nuclei, a, b and c can each be an integer from 1 to 8, ie up to 3 times the number of aromatic nuclei present (2 for naphthalene). In the three-nuclear Ar part, a, b
And c can each be an integer from 1 to 12. For example, when Ar is a biphenyl moiety or a naphthyl moiety,
a, b and c may each independently be an integer of 1-8. The values of a, b and c are obviously limited by the fact that their sum cannot exceed the total number of unsatisfied valences of Ar.

A single-ring aromatic nucleus that can be an Ar moiety can be represented by the general formula: ar (Q) _m where ar is a single-ring aromatic nucleus having 4 to 10 carbons ( For example, benzene), each Q independently represents a lower alkyl group, a lower alkoxy group, a nitro group, or a halogen atom, and m is 0-3. As used herein and in the appended claims, "lower" refers to groups having 7 or fewer carbon atoms (eg, lower alkyl groups and lower alkoxyl groups). Halogen atoms include fluorine, chlorine, bromine and iodine atoms; usually the halogen atoms are fluorine and chlorine atoms.

Specific examples of single ring Ar moieties include:

[0169]

[Chemical 42]

Etc.

Here, Me is methyl, Et is ethyl, and Pr is n-.
Propyl, and Nit are nitro. When Ar is a polynuclear fused ring aromatic moiety, it may be represented by the general formula:

[0172]

[Chemical 43]

Where ar, Q and m are the same as defined above, m'is 1 to 4, and

[0174]

[Chemical 44]

Represents a pair of fused bonds that fuse two rings so that the two carbon atoms become part of the rings of each two adjacent rings. Specific examples of fused ring aromatic moieties Ar include:

[0176]

[Chemical formula 45]

Etc.

When the aromatic moiety Ar is a linked polynuclear aromatic moiety, it can be represented by the general formula: ar (Lng-ar) _w (Q) _mw where w is 1 to about 20. Where ar is the same as described above, except that there are at least three unsatisfied (ie, free) valences in the entire ar group.
Q and m are the same as defined above. Each Lng
Are bridging bonds individually selected from the group consisting of: carbon-carbon single bond, ether bond (eg -O
-), A keto bond (e.g.,

[0179]

[Chemical formula 46]

), A sulfide bond (eg, -S-),
Polysulfide bond having 2 to 6 sulfur atoms (for example, -S- _2-6 ), sulfinyl bond (for example, -S- _2-6 )
S (O) -), sulfonyl linkages _{(e.g., -S (O) 2 -)} , lower alkylene linkages _{(e.g., -CH 2 -, - CH 2} -CH 2 -,

[0181]

[Chemical 47]

[0182] etc.), di (lower alkyl) methylene linkages (e.g., CR ^O ₂ -), lower alkylene ether linkages _{(e.g., -CH 2 O -, - CH} 2 O-CH 2 -, - CH 2 -CH 2 O-, -CH
₂ CH ₂ OCH ₂ CH ₂ −,

[0183]

[Chemical 48]

Etc.), a lower alkylene sulfide bond (eg, where one or more —O— in this lower alkylene ether bond is replaced by an —S— atom), a lower alkylene polysulfide bond (eg, Here, one or more -O- is -S- _2-6.
Replaced by a group), an amino bond (eg,

[0185]

[Chemical 49]

Here, alk is lower alkylene or the like), polyamino bond (eg,

[0187]

[Chemical 50]

Where the unfilled free N valences are occupied by H atoms or R 2 ^O groups), and mixtures of such crosslinks, each R 2 ^O being a lower alkyl group. In the aromatic moiety attached above, one or more ar groups are attached to a condensation nucleus (eg,

[0189]

[Chemical 51]

It is also possible to substitute Specific examples of attached moieties include:

[0191]

[Chemical 52]

Etc.

Usually, all of these Ar moieties have R groups, --OH.
It has no substituents other than the group and the -NH ₂ group (and any bridging group). For reasons such as price, availability, performance, etc., this Ar moiety is usually a benzene nucleus, a lower alkylene bridged benzene nucleus, or a naphthalene nucleus. Therefore, a typical Ar moiety has a benzene nucleus or naphthalene having 3 to 5 unsatisfied valences such that one or two unsatisfied valences can be satisfied with a hydroxyl group. The remaining unfilled valences, which are nuclei, are in either the ortho or para positions relative to the hydroxyl groups, if possible. Preferably, Ar has at least three unfilled valences, one is filled with a hydroxyl group and the remaining two or three are in either the ortho or para position relative to the hydroxyl group. It is a benzene nucleus, as in.

Substantially Saturated Hydrocarbon-Based Group R ⁹ The aminophenols of the present invention contain a substantially saturated monovalent hydrocarbon-based group having at least about 10 aliphatic carbon atoms. The group is directly attached to the aromatic moiety Ar. The R ⁹ group can have up to about 400 aliphatic carbon atoms. More than one such group may be present, but usually there will be no more than two or three such groups for each aromatic nucleus of this aromatic nucleus moiety Ar. Existing R ⁹
The total number of groups is indicated by the "a" value in formula II. Generally, the hydrocarbon-based group will contain from at least about 30, and more typically, at least about 50 aliphatic carbon atoms to about
It has up to 750, and more typically up to about 300 aliphatic carbon atoms.

Generally, the hydrocarbon-based radical R ⁹ is 2
And olefins having 1 to 10 carbon atoms (eg ethylene, propylene, butene-1,
Isobutene, butadiene, isoprene, 1-hexene, 1-
Octene and the like) or interpolymers (eg, copolymers, terpolymers).
Typically, these olefins are 1-monoolefins such as ethylene homopolymers. The R ⁹ group can also be derived from halogenated (eg, chlorinated or brominated) analogs of such homopolymers or interpolymers. However, this R ⁹
The group can be used for other raw materials such as monomeric high molecular weight alkenes (eg 1-tetracontene) and their chlorinated and hydrochlorinated analogues, aliphatic petroleum fractions (especially paraffin wax). , And their decomposed and chlorinated analogs and hydrochlorinated analogs), white oils, synthetic alkenes (eg, those produced by the Ziegler-Natta process (eg, poly (ethylene) grease)), and It may be manufactured from other raw materials known to those skilled in the art. Any unsaturation in the R ⁹ group can be reduced or removed by hydrogenation, according to methods well known in the art, before the nitration step described below.

As used herein, within the context of this invention, the term "hydrocarbyl-based" refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon-like properties. Show. Thus, a hydrocarbon-based group may contain up to 1 non-hydrocarbon group for each 10 carbon atoms provided that this non-hydrocarbon group significantly determines the predominant hydrocarbon character of the group. There is a condition not to change. Those skilled in the art are aware of such groups and include, for example, hydroxyl, halo (particularly chloro and fluoro), alkoxyl, alkylmercapto, alkylsulfoxy and the like. However, the hydrocarbon-based radical R ⁹ is usually pure hydrocarbyl and does not contain such non-hydrocarbon radicals. The hydrocarbon-based radical R ⁹ is substantially saturated. Substantially saturated means that the group contains less than one carbon-carbon unsaturated bond for each ten carbon-carbon single bonds present. Generally, these groups contain less than one carbon-carbon non-aromatic unsaturated bond for each 50 carbon-carbon bonds present.

The hydrocarbon-based groups of the aminophenols of the present invention are also substantially aliphatic in nature. That is, these groups are not more than one non-aliphatic moiety (cycloalkyl group, cycloalkenyl group or aromatic group) having not more than 6 carbon atoms for each 10 carbon atoms in this R ⁹ group. ) Is included. However, usually this R ⁹ group is
For each 50 carbon atoms, it contains no more than one such non-aliphatic group, and often these groups do not contain any such non-aliphatic group. Ie this typical
The R ⁹ group is purely aliphatic. Typically, these pure aliphatic groups R ⁹ are alkyl or alkenyl groups. Specific examples of substantially saturated hydrocarbon-based groups R ⁹ include: tetra (propylene) group, tri (isobutene) group, tetracontanyl group, hempentacontanyl group, about 35 to about
Poly (ethylene / propylene) with 70 carbon atoms
A mixture of groups, a mixture of oxidatively or mechanically degraded poly (ethylene / propylene) groups having from about 35 to about 70 carbon atoms, a poly (propylene) having from about 80 to about 150 carbon atoms. / 1-hexene) mixture, 20 pieces and 32
A mixture of poly (isobutene) groups having between 40 carbon atoms, a mixture of poly (isobutene) groups having an average of 50 to 75 carbon atoms.

A preferred source of R ⁹ groups is a butene content of 35% to 75% by weight and a content of 15% to 60% by weight in the presence of a Lewis acid catalyst (eg aluminum trichloride or boron trifluoride). Is a poly (isobutene) obtained by polymerizing a C ₄ purified stream having an isobutene content of These polybutenes contain predominantly (in greater than 80% of the total repeat units) isobutene repeat units of the following configurations:

[0199]

[Chemical 53]

Aromatic Part Ar of the Aminophenol of the Present Invention
The attachment of the hydrocarbon-based group R ⁹ to can be done by a number of methods well known to those skilled in the art. One particularly suitable method is the Friedel-Crafts reaction, where olefins (eg, polymers containing olefinic bonds), or their hydrogenated or halohydrogenated analogs, are reacted with phenols. react. This reaction occurs in the presence of a Lewis acid catalyst (eg, boron trifluoride and its complexes with ethers, phenols, hydrogen fluoride, aluminum chloride, aluminum bromide, zinc dichloride, etc.). The method and conditions for carrying out such a reaction are
It is well known to those skilled in the art. For example, "Kirk-Osmer (Kir
(K-Othmer) Encyclopedia of Chemical Technology, "Phenol Alkylation" in the paper titled "Phenol Alkylation" (2nd ed., Vol. 894-895, Interscience Publishing, John Willey and Company Division, New York, 1963). Other similarly suitable and convenient methods of attaching the hydrocarbon-based group R ⁹ to the aromatic moiety Ar will be readily envisioned by those skilled in the art.

As can be seen from a discussion of Formula II, the aminophenols of the present invention include at least one of the following substituents:
Containing: a hydroxyl group, a R ⁹ group as defined above, and a primary amino group, —NH ₂ . Each of the above groups must be attached to a carbon atom that is part of the aromatic nucleus of the Ar moiety. However, if more than one aromatic nucleus is present in this Ar moiety, they need not each be attached to the same aromatic ring.

In a preferred embodiment, the aminophenols of the present invention contain one each of the above substituents (ie, a, b and c are each 1) but a single aromatic ring, most preferably Is benzene. A preferred class of aminophenols may be represented by the formula:

[0203]

[Chemical 54]

The R ⁹ group herein is a substantially saturated hydrocarbon-based group having from about 30 to about 400 aliphatic carbon atoms and is located in the ortho or para position relative to the hydroxyl group. ing. R ⁶ is a lower alkyl group, a lower alkoxyl group, a nitro group or a halogen atom, and z is 0 or 1. Usually z is 0, and R ⁹ is
It is a substantially saturated pure hydrocarbyl aliphatic group.
Often, R ⁹ is an alkyl or alkenyl group para position relative to -OH substituent. Often, in these preferred aminophenols, one only amino groups, i.e., -NH although ₂ is present, may be present two.

In a further preferred embodiment of the invention the aminophenol has the formula:

[0206]

[Chemical 55]

Wherein R ⁹ is derived from a homopolymerized or interpolymerized C _2-10 1-olefin and has, on average, from about 30 to about 400 aliphatic carbon atoms, And R ⁶ and z are the same as defined above. Usually R ⁹ is derived from ethylene, propylene, butylene and mixtures thereof. Typically R ⁹ is
Derived from polymerized butenes. Often R ⁹ has at least about 50 aliphatic carbon atoms and z is 0.

The aminophenols of the present invention can be prepared by a number of synthetic routes. These routes can be varied depending on the type of reaction used and the order used. For example, aromatic hydrocarbons (eg, benzene) are
It can be alkylated with an alkylating agent such as a polymerized olefin to form an alkylated aromatic intermediate. This intermediate can then be nitrated, for example, to form a polynitro intermediate. The polynitro intermediate is sequentially reduced to a diamine, then diazotized and reacted with water to convert one of the amino groups to a hydroxyl group to give the desired aminophenol. On the other hand, one nitro group in this polynitro intermediate is converted to a hydroxyl group by melting with caustic to give a hydroxynitroalkylated aromatic compound, which is then reduced to give the desired aminophenol. Is obtained.

Another useful route to the aminophenols of the present invention involves the alkylation of phenols with olefinic alkylating agents to form alkylated phenols. The alkylated phenol is then nitrated to form the intermediate nitrophenol, which can be converted to the desired aminophenol by reducing at least some of the nitro groups to amino groups.

The method for alkylating phenol is Kirk-
It is disclosed in the above mentioned article of "Encyclopedia of Chemical Technology" by Kirk-Othmer and is well known to those skilled in the art. The method of nitration of phenol is also
It is well known. For example, Kirk-Othmer
"Encyclopedia of Chemical Technology" (2nd edition, volume 13) entitled "Nitrophenol" (page 888 and below), as well as "Aromatic substitution; nitration and halogenation" (PBD Delamore) (De La
Mare) and JH Ridd; New York
Academic Press, 1959); "Nitration and Aromatic Reactivity" (by JG Hogget; London, Cambridge University Press, 1961); and "Nitro and Nitroso Chemistry" (Henry Foyer).
(Henry Feuer), Interscience Publishing, New York, 1969).

Aromatic hydroxy compounds can be nitrated with nitric acid, mixtures of nitric acid with other acids such as sulfuric acid or boron trifluoride, nitric tetroxide, nitronium tetrafluoroborate and acyl nitrates. Generally, for example, nitric acid at a concentration of about 30% to 90% is a convenient nitrating reagent. Substantially inert liquid diluents and solvents such as acetic acid or butyric acid can improve the contact of the reagents and thus facilitate the reaction. The conditions and concentrations for nitrating hydroxyaromatic compounds are also
Known in the art. For example, the reaction can be performed at a temperature of about -15 ° C to about 150 ° C. Usually, the nitration is conveniently carried out between about 25 and 75 ° C.

Generally, depending on the particular nitrating agent, about 0.5 to 4 moles of nitrating agent are used for each mole of aromatic nucleus present in the hydroxyaromatic intermediate to be nitrated. If there is more than one aromatic nucleus in the Ar part,
The amount of nitrating agent can be increased proportionally according to the number of such nuclei present. For example, one mole of a naphthalene-based aromatic intermediate has an equivalent weight of two "single ring" aromatic nuclei for purposes of this invention, and about 1 to 4 moles of nitrating agent is generally used. When nitric acid is used as the nitrating agent, usually about 1.0 to about 3.0 mol of nitric acid is used per mol of the aromatic nucleus. If you want to proceed or accelerate the reaction (per “single ring” aromatic nucleus),
Up to about 5 molar excess of nitrating agent can be used.

Although it is convenient to react the nitration mixture for an extended period of time (eg 96 hours), the nitration of the hydroxyaromatic intermediate generally takes 0.25 to 24 hours.

Reduction of aromatic nitrogen compounds to the corresponding amines is also well known. For example, Kirk-Osmer
See the article entitled "Amination by Reduction" in "Encyclopedia of Chemical Technology" (2nd edition, Volume 2, pages 76-99) by K-Othmer). In general, such reduction is carried out in the presence of a metal catalyst (eg palladium, platinum and its oxides, nickel, copper chromite, etc.) with, for example, hydrogen, carbon monoxide or hydrazine (or mixtures thereof). Can be done. The cocatalyst (eg, alkali metal or alkaline earth metal hydroxide or amine (including aminophenol)) is
It can be used in the reduction with these catalysts.

The reduction can also be carried out by using a reduced metal in the presence of an acid (eg hydrochloric acid). Typical reducing metals include zinc, iron and tin, and salts of these metals can also be used.

The nitro group can also be reduced by the Zinin reaction. This is discussed in "Organic Reactions" (Vol. 20, John Wiley & Sons, New York, 1973, p. 455 et seq.). Generally, this ginine reaction involves reduction of the nitro group with a divalent, negative sulfur-containing compound such as alkali metal sulfides, polysulfides and hydrosulfides.

This nitro group can be reduced by electrolytic action. See, for example, the "Reductive Amination" paper cited above.

The aminophenols of the invention are typically obtained by reduction of nitrophenol with hydrogen in the presence of a metal catalyst as described above. This reduction is generally at a temperature of about 15 ° C to 250 ° C, typically about 50 ° C.
A temperature of ℃ to 150 ℃, and a hydrogen pressure of about 0 to 2000 psig.
Typically, it is carried out at a hydrogen pressure of about 50-250 psig.
The reaction time for reduction is usually varied between about 0.5 and 50 hours. Substantially inert liquid diluents and solvents such as ethanol, cyclohexane and the like can be used to facilitate the reaction. This aminophenol product is obtained by well-known methods (for example, distillation, filtration, extraction, etc.).

The reduction is carried out until at least about 50%, usually about 80% of the nitro groups in the nitro intermediate mixture have been converted to amino groups. A typical pathway for forming the aminophenols of the invention described herein can be summarized as follows: (I) Nitrating at least one compound of the formula: with at least one nitrating agent. :

[0220]

[Chemical 56]

Where R ⁴ is a substantially saturated hydrocarbon-based radical having at least 10 aliphatic carbon atoms; a and c are each independently an aromatic odor present in Ar ′. It is an integer from 1 to 3 times the number of nuclei, provided that the sum of a and c does not exceed the unsatisfied valence of Ar '; and Ar' is (a) and ( An aromatic moiety having 0 to 3 optional substituents selected from the group consisting of the following under the conditions of b): lower alkyl, lower alkoxyl, nitro and halo, or any two or more. The combination of substituents of: (a) Ar 'has at least one hydrogen atom directly bonded to a carbon atom that is part of the aromatic nucleus, and (b) Ar' is one hydroxyl group and When benzene has only one R ⁴ substituent,
The R ⁴ substituent is in the ortho or para position with the hydroxyl substituent forming the first reaction mixture containing the nitro intermediate; and (II) at least about 50 in the first reaction mixture. % Reduction of nitro groups to amino groups.

Generally, this means reducing at least about 50% of the nitro groups to amino groups in a compound or mixture of compounds of the formula:

[0223]

[Chemical 57]

Wherein R ⁴ is a substantially saturated hydrocarbon-based substituent having at least 10 aliphatic carbon atoms; a, b and c are each independently an aromatic fragrance present in Ar. It is an integer from 1 to 3 times the number of nuclei, provided that the sum of a, b and c does not exceed the unsatisfied valence of Ar; and Ar is: An aromatic moiety having 0 to 3 optional substituents selected from the group consisting of: lower alkyl, lower alkoxyl, halo, or a combination of two or more optional substituents: Ar is 1 when benzene having only pieces of hydroxyl and one R ⁴ substituent, the R ⁴ substituent, and said hydroxyl substituent is in the ortho position or para position.

Component (A) and (B) (I), or component (A),
The compositions of the present invention containing (B) and (C) are useful in two stroke cycle engines. When this composition contains (A) and (B) (I), these components are about 97: 3.
To about 80:20 by weight, preferably 95: 5 to about 85:15 by weight, most preferably about 93: 7 to about 88:12. When the composition contains (A), (B) and (C), these components are present in the following parts by weight: Components Generally preferred and most preferred (A) 70-94 76-94 80 -90 (B) 5-18 3-12 5-10 (C) 1-12 1-7.5 3-6 The components of the present invention are mixed and dissolved together according to the above range. It is understood that other ingredients than those listed above may be present in the two-stroke cycle preparation.

[0226]

EXAMPLES The following specific illustrative examples describe how to make the detergents / dispersants and aminophenols that make up components (B) and (C) of the present invention. Not only in these examples, but in this specification and the appended claims,
All percentages, parts and ratios are by weight, unless explicitly stated otherwise. Temperatures are in degrees Celsius (° C), unless explicitly stated otherwise.
Is.

Example 1A 4578 parts polyisobutene-substituted phenol, which was prepared by alkylation with boron trifluoride-phenol catalyst with polyisobutene having a number average molecular weight of about 1000 (vapor phase permeation method). , 3052 parts mineral oil diluent and 72 fiber spirits
Heat 5 parts of the mixture to 60 ° C. to homogenize. After cooling to 30 ° C., 319.5 parts of 16 molar nitric acid in 600 parts of water are added to this mixture. Cooling is required to maintain the temperature of this mixture below 40 ° C. The reaction mixture is stirred for a further 2 hours and then aliquots of 3,710 parts are transferred to a second reaction vessel.
This second part is treated at 25-30 ° C. with an additional 127.8 parts of 16 molar nitric acid in 130 parts of water. The reaction mixture is stirred for 1.5 hours and then stripped to 220 ° C / 30 tor. Filtration gives an oil solution of the desired intermediate (IA).

Example 1B Intermediate (1A) as described in Example 1A
A mixture of 810 parts of the oil solution of (4), 405 parts of isopropyl alcohol and 405 parts of toluene is charged into an autoclave of an appropriate size. Platinum oxide catalyst (0.81 parts) is added and the autoclave is evacuated 4 times and purged with nitrogen to remove any residual air. 29 to 55 psi in this autoclave
Supply hydrogen at a pressure of g. During this time, the contents are stirred and heated to 27-92 ° C for a total of 13 hours. Four
Residual excess hydrogen is removed from the reaction mixture by two evacuations and a nitrogen purge. The reaction mixture is then filtered through diatomaceous earth and the filtrate stripped to give an oil solution of the desired aminophenol. This solution contains 0.578% nitrogen.

Example 2 906 parts of an oil solution of alkylphenyl sulfonic acid (which has an average molecular weight of 450 by vapor phase permeation method), 564 parts of mineral oil, 600 parts of toluene,
78 in a mixture of 98.7 parts magnesium oxide and 120 parts water.
Blow carbon dioxide at a rate of about 3 cubic feet per hour for 7 hours at a temperature of ~ 85 ° C. The reaction mixture is constantly stirred throughout the carbonation. After carbonation, the reaction mixture is stripped to 165 ° C / 20 torr. And the residue is filtered. The filtrate is an oil solution of the desired overbased magnesium sulfonate having a metal ratio of about 3.

(Example 3) Chlorinated poly (isobutene)
(This has an average chlorine content of 4.3%, and an average of 8%
Having 2 carbon atoms) and maleic anhydride, about 200
Polyisobutenyl succinic anhydride is prepared by reacting at ° C. The polyisobutenyl succinic anhydride obtained has a saponification number of 90. This succinic anhydride 1,246
To a mixture of 1 part and 1000 parts toluene, at 25 ° C., add 76.6 parts barium oxide. Heat the mixture to 115 ° C.,
Then 125 parts of water are added drop by drop over 1 hour. The mixture is then refluxed at 150 ° C. until all the barium oxide has reacted. Stripping and filtration give a filtrate with a barium content of 4.71%.

Example 4 Chlorinated poly (isobutene)
1500 parts (which has a molecular weight of about 950 and a chlorine content of 5.6%), an alkylene polyamine 285 having an average composition stoichiometrically equivalent to tetraethylene pentamine.
Part and 1200 parts of benzene are heated to reflux. While removing benzene, the temperature of this mixture was
Then slowly heat to 170 ° C. for 4 hours. The cooled mixture is diluted with an equal volume of mixed hexane and absolute ethanol (1: 1). The mixture is heated to reflux and 1/3 volume of 10% aqueous calcium carbonate solution is added. After stirring, the mixture is cooled and the phases are separated.
The organic phase is washed with water and stripped to give the desired polyisobutenyl polyamine with a nitrogen content of 4.5%.

Example 5 140 parts toluene, 400 parts polyisobutenyl succinic anhydride having a saponification number of 109 (prepared from poly (isobutene) having a molecular weight of about 850 by vapor phase permeation), and A mixture of 63.6 parts of an ethyleneamine mixture having an average composition stoichiometrically corresponding to tetraethylenepentamine is heated to 150 ° C. while removing the water / toluene azeotrope. The reaction mixture is then heated under reduced pressure to 150 ° C. until the distillation of toluene is complete. This residual acylated polyamine has a nitrogen content of 4.7%.

Example 6 To 1,133 parts of commercially available diethylenetriamine heated at 110-150 ° C. is slowly added 6820 parts of isostearic acid over 2 hours. The mixture is held at 150 ° C for 1 hour and then heated to 180 ° C for an additional hour. Finally, add 0.5 of this mixture.
Heat to 205 ° C for hours. During this heating, the mixture is blown with nitrogen to remove volatiles. This mixture was held at 205-230 ° C for a total of 11.5 hours,
Then, stripping at 230 ℃ / 20 torr gives 6.2
The desired acylated polyamine is obtained as a residue containing% nitrogen.

Example 7 50 parts polypropyl-substituted phenol (which has a molecular weight of about 900 by vapor phase infiltration), mineral oil (solvent-refined paraffin oil having a viscosity of 100 SUS at 100 ° F.) 500 parts , And a mixture of 130 parts of a 9.5% aqueous dimethylamine solution (equivalent to 12 parts of amine), 22 parts of a 37% aqueous formaldehyde solution (equivalent to 8 parts of aldehyde) are added dropwise over a period of 1 hour. During the addition, the reaction temperature is slowly raised to 100 ° C. and the mixture is blown with nitrogen and kept at this temperature for 3 hours.
100 parts of toluene and 50 parts of mixed butyl alcohol are added to the cooled reaction mixture. The organic phase is washed 3 times with litmus paper until neutral, filtered and the organic phase 20
Stripping is performed at 0 ° C / 5 to 10 torr. This residue is an oil solution of the final product containing 0.45% nitrogen.

(Example 8) Mineral oil 140 parts (by weight), 105
Poly (isobutene) with a saponification value of (molecular weight 100
0) A mixture of 174 parts of substituted succinic anhydride and 23 parts of isostearic acid is prepared at 90 ° C. To this mixture, 80 ℃ ~ 10
A mixture of polyalkyleneamines with a total composition corresponding to tetraethylenepentamine over 1.3 hours at 0 ° C.
Add 17.6 parts. This reaction is exothermic. Add 22 pounds to this mixture at a rate of 5 pounds per hour for 3 hours.
Blowing with nitrogen at 5 ° C. gives 47 parts of aqueous distillate.
The mixture was dried at 225 ° C for 1 hour, cooled to 110 ° C,
Then filtration gives an oil solution of the desired end product.

The present invention also contemplates the use of other additives in the lubricating oil composition of the present invention. These other additives include antioxidants, extreme pressure agents, corrosion inhibitors, pour point depressants,
Included are conventional types of additives such as color stabilizers, defoamers, and other additive materials commonly known to those skilled in the art of preparing lubricating oil compositions.

Dyes can be used for verification purposes to indicate whether the two-stroke cycle fuel contains a lubricant. Coupling agents such as organic surfactants are incorporated into certain products to improve component solubility and improve the water resistance of the fuel / lubricant mixture.

Antiwear and lubricity improvers are used for very high fuel / lubricant ratios in certain applications (eg racing). Lead scavengers or combustion chamber deposit modifiers are sometimes used to extend spark plug life and remove carbon deposits. Halogenated compounds and / or phosphorus-containing materials can be used for this application.

All types of rust inhibitors and corrosion inhibitors can be incorporated into the two stroke cycle oil formulations. Fragrances or deodorants are sometimes used for sensory reasons.

Lubricating agents such as synthetic polymers (eg, polyisobutene having a number average molecular weight in the range of about 500 to about 10,000 as measured by vapor phase permeation or gel permeation chromatography), polyol ethers (eg, poly ( Oxyethylene-oxypropylene) ether) oils and ester oils (for example the ester oils mentioned above)
May also be used in the oil composition of the present invention. Natural oil fractions such as bright stock, a relatively viscous product formed during the manufacture of conventional lubricating oils from petroleum, can also be used for this purpose. These are usually present in the two-stroke cycle oil in an amount of about 3 to about 20% of the total oil composition.

Diluents such as petroleum naphtha or about 38 to
Low molecular weight esters with boiling points in the range of 90 ° C (eg,
Stodard solvent) may also be included in the oil composition of the present invention, typically in an amount of 5 to 25%. Diluent
When used as a direct replacement for (A), 10 parts of (A) are replaced with 10 parts of diluent.

Table 2 describes some exemplary biodegradable two-stroke cycle engine oil lubricant compositions of the present invention.

[0243]

[Table 2]

In some two-stroke cycle engines, this lubricating oil may be injected with the fuel directly into the intake manifold or crankcase, or directly into the fuel, just before the fuel enters the combustion chamber. The two-stroke cycle lubricant of the present invention may be used in this type of engine.

As is well known to those skilled in the art, two-stroke cycle engine lubricating oils are often added directly to the fuel to form a mixture of oil and fuel, which mixture is then introduced into the engine cylinder. Such lubricant-fuel oil mixtures are within the scope of this invention.
Such lubricant-fuel formulations generally contain from about 15 to 250 parts of fuel per part of oil, typically from about 50 to 100 parts of fuel per part of oil.

Fuels used in two-stroke cycle engines are well known to those of ordinary skill in the art, and typically have a major proportion of normally liquid fuels, such as hydrocarbonaceous petroleum distillate fuels (eg, ASTM specification D-439-. Automobile gasoline defined by 73). Such fuels may also contain non-hydrocarbon substances such as alcohols, ethers, organic nitro compounds and the like (eg methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane). Also within the scope of the invention are liquid fuels derived from plant or mineral sources such as corn, alfalfa, shale and coal. Examples of such fuel mixtures include blends of gasoline and ethanol, blends of diesel fuel and ether, blends of gasoline and nitromethane, and the like. Gasoline, that is, ASTM at 60 ° C at 10% distillation point to 205 ° C at 90% distillation point
Mixtures of hydrocarbons having a boiling point are particularly preferred.

Two-stroke cycle fuels also contain other additives well known to those skilled in the art. These include anti-knock agents (eg tetraalkyl lead compounds), lead scavengers (eg haloalkanes (eg ethylene dichloride and ethylene dibromide)), octane number enhancers (eg methyl-t).
-Butyl ether (MTBE), ethyl-t-butyl ether (ETB
E) and aromatic compounds (eg xylene and toluene), dyes, antioxidants (eg 2,6-di-tert-butyl-4-methylphenol), rust inhibitors (eg alkylated amber) Acid and its anhydride), antibacterial agent, anti-gumming agent, metal deactivator, demulsifier, upper cylinder lubricant, anti-icing agent and the like.

An example of a lubricant-fuel composition encompassed by the present invention is a mixture of automotive gasoline and the above lubricant formulation of Example C, wherein 25 parts gasoline per part lubricant.
Some have a ratio of 200 parts (by weight).

Concentrates containing the nitrogen-containing soluble composition of the present invention are also within the scope of the present invention. These concentrates typically contain from about 20 to about 1 of the above natural oils.
80%, and from about 20 to about 80% of one or more nitrogen-containing soluble compositions. As one of ordinary skill in the art will readily appreciate, such concentrates also include various types of concentrates.
It may contain one or more of the above auxiliary additives.

Many tests for two-stroke cycle applications are done in comparison to a reference oil of suitable quality. Therefore, for example, in the Yamaha CE50S lubrication test,
The goal is to obtain a torque reduction that is less than or equal to the reference oil (the lower this number, the better the lubricity).

Example J Product of Example A (oil)
A fuel: oil 150: 1 blend is prepared by adding 100 parts to 15,000 parts gasoline (fuel). The torque drop on the Yamaha CE50S is 4.75 and the torque drop for the reference two-stroke cycle preparation with a fuel to oil ratio of 150: 1 is 6.26.

Although the present invention has been described in terms of its preferred embodiment, it is to be understood that various modifications thereof will be apparent to those of ordinary skill in the art upon reading this specification. Therefore, it should be understood that the invention disclosed herein is intended to include those modifications that fall within the scope of the appended claims.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C10M 101: 04 133: 16 105: 38 133: 04 133: 14 129: 26 135: 10 129: 10 159: 20 133: 50) C10N 10:02 10:04 30:04 40:26 70:00

Claims (58)

[Claims] 1. A nitrogen-containing soluble organic composition having the following formulation of (A) and (B): (A) At least one natural oil including animal or vegetable oils containing triglycerides of the formula: [Chemical 1] Wherein R ¹ , R ² and R ³ are independently saturated or unsaturated aliphatic hydrocarbyl groups containing from about 8 to about 24 carbon atoms; and (B) (I) at least 10 A detergent / dispersant containing at least one acylated nitrogen-containing compound having a substituent having an aliphatic carbon atom, the compound comprising a carboxylic acylating agent and at least one -NH group. Manufactured by reacting with at least one amino compound containing ## STR3 ## wherein the acylating agent is bonded to the amino compound via an imide bond, an amide bond, an amidine bond or an acyloxyammonium bond. 2. The natural oil includes vegetable oil.
Composition. 3. The vegetable oil is soybean oil, rapeseed oil, high oleic rapeseed oil, sunflower oil, high oleic sunflower oil, coconut oil, corn oil, peanut oil, sawarawa oil, palm oil, high oleic corn oil, Palm kernel oil, meadowfoam oil, les clera (lesqu
The composition of claim 2 comprising erella oil and vernonia oil. 4. The composition of claim 1 wherein said natural oil is an animal oil including lard oil or tallow oil. 5. R ¹ , R ² and R ³ are independently from about 12 to about.
The composition of claim 1 containing 22 carbon atoms. 6. The vegetable oil is high oleic sunflower oil,
The composition of claim 3 comprising high oleic safflower oil, high oleic corn oil or high oleic rapeseed oil. 7. The detergent / dispersant (B) has at least one substituent having a substituent having at least 10 aliphatic carbon atoms.
An acylated nitrogen-containing compound, the compound being produced by reacting a carboxylic acid acylating agent with at least one amino compound containing at least one —NH group. The composition according to claim 1, wherein is bonded to the amino compound via an imide bond, an amide bond, an amidine bond or an acyloxyammonium bond. 8. The composition of claim 7 wherein said amino compound is an alkylene polyamine of the general formula: embedded image Where U is an alkylene group having 2 to 10 carbon atoms; each R ⁸ is independently a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group, provided that at least one R 8 is ⁸ is a hydrogen atom, and n is 1-10. 9. The composition of claim 8 wherein said acylating agent is a monocarboxylic or polycarboxylic acid or equivalent reactant containing an aliphatic hydrocarbyl substituent having at least about 30 carbon atoms. object. 10. The composition of claim 9 wherein the substituents are prepared from homopolymers or interpolymers of C _2-10 1-monoolefins or mixtures thereof. 11. The composition of claim 10 wherein said homopolymer or interpolymer is a homopolymer or interpolymer of ethylene, propylene, 1-butene, 2-butene, isobutene or mixtures thereof. 12. The composition of claim 8 wherein said acylating agent is at least one monocarboxylic acid having 12 to 30 carbon atoms or their equivalent reactants. 13. The composition of claim 12 wherein said acylating agent is a mixture of fatty monocarboxylic acids or their equivalent reactants having straight or branched carbon chains. 14. The ethylene compound, wherein the amino compound has at least 2 to about 8 amino groups,
Propylene polyamine or trimethylene polyamine,
Or a mixture of such polyamines.
Composition. 15. The weight ratio of (A) :( B) (I) is about 97: 3.
The composition of claim 1 in the range of to about 80:20. 16. A nitrogen-containing soluble organic composition having the following combination of (A), (B) and (C): (A) at least one including animal or vegetable oils containing triglycerides of the formula: Natural oil of: Wherein R ¹ , R ² and R ³ are independently saturated or unsaturated aliphatic hydrocarbyl groups containing from about 8 to about 24 carbon atoms; (B) the following (I), ( II), at least one detergent / dispersant selected from the group consisting of (III) and (IV): (I) at least one acylation with a substituent having at least 10 aliphatic carbon atoms A nitrogen-containing compound, which is prepared by reacting a carboxylic acylating agent with at least one amino compound containing at least one -NH group, the acylating agent comprising:
Bound to the amino compound via an imide bond, an amide bond, an amidine bond or an acyloxyammonium bond; (II) at least one neutral or basic metal salt of an organic sulfur-containing acid, phenol or carboxylic acid; (III) at least one hydrocarbyl-substituted amine, wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 12 carbon atoms,
Provided that the amine is not an aminophenol (C); and (IV) at least one nitrogen-containing condensate of a phenol compound, an aldehyde compound and an amino compound having at least one -NH group; and (C) At least one aminophenol of the following general formula: Where R ⁴ is a substantially saturated hydrocarbon-based substituent having at least 10 aliphatic carbon atoms; a, b and c are each independently the number of aromatic nuclei present in Ar. Is an integer from 1 to 3 times, provided that the sum of a, b and c does not exceed the unsaturated valence of Ar; and Ar
Is lower alkyl, lower alkoxyl, nitro, halo,
Alternatively, it is an aromatic moiety having 0 to 3 optional substituents selected from the group consisting of a combination of two or more of these substituents. 17. The composition of claim 16 wherein said natural oil comprises vegetable oil. 18. The vegetable oil is soybean oil, rapeseed oil, high oleic rapeseed oil, sunflower oil, high oleic sunflower oil, coconut oil, peanut oil, sourdough oil, high oleic acid safflower oil, palm oil, corn oil. , High oleic acid corn oil, palm kernel oil, meadow foam (meadowf
oam oil, lesquerella oil and vernonia
18. The composition of claim 17, which comprises (vernonia) oil. 19. The composition of claim 16 wherein said natural oil is an animal oil including lard oil or tallow oil. 20. R ¹ , R ² and R ³ are independently about 12 to
17. The composition of claim 16 containing about 22 carbon atoms. 21. The vegetable oil includes high oleic sunflower oil, high oleic safflower oil, high oleic corn oil or high oleic rapeseed oil.
The composition of 8. 22. R ⁴ contains up to about 750 carbon atoms and there is no optional substituent attached to Ar.
Composition. 23. The composition according to claim 22, wherein R ⁴ is an alkyl group or an alkenyl group. 24. The composition of claim 16 wherein R ⁴ contains from about 30 to about 750 aliphatic carbon atoms and is prepared from a homopolymer or interpolymer of C _{2 to} C ₁₀ olefins. 25. The composition of claim 24, wherein said olefin is selected from the group consisting of ethylene, propylene, butylene and mixtures thereof. 26. a, b and c are each 1;
17. The composition of claim 16, wherein there are no optional substituents attached to Ar and Ar is a benzene nucleus. 27. R ⁴ is from at least 30 carbon atoms to about
Alkyl is a group or an alkenyl group, the composition of claim 26 which is derived from homo- or interpolymers of C ₂ -C ₁₀ 1-monoolefins having up to 750 carbon atoms. 28. The composition of claim 16 wherein said aminophenol is an aminophenol of the formula: Where R ⁵ is a substantially saturated hydrocarbon-based substituent having an average of about 30 to about 400 aliphatic carbon atoms, R ⁶ is lower alkyl, lower alkoxy, nitro and halo. An element selected from the group consisting of; and z
Is 0 or 1. 29. A polymer of olefins wherein R ⁵ is a pure hydrocarbyl aliphatic group having at least about 50 carbon atoms and is selected from the group consisting of C _2-10 1-monoolefins and mixtures thereof. 29. The composition of claim 28, which is also made from an interpolymer. 30. The composition of claim 29, wherein z is 0. 31. The composition of claim 16 wherein said detergent / dispersant is (II) at least one neutral or basic metal salt of an organic sulfur-containing acid, phenol or carboxylic acid. 32. The composition of claim 31, wherein the detergent / dispersant is at least one basic metal salt of an organic sulfonic acid or phenol. 33. The composition of claim 32, wherein said metal is at least one alkali metal or alkaline earth metal. 34. The composition of claim 32, wherein the detergent / dispersant is at least one alkaline earth metal sulfonate. 35. The composition of claim 34, wherein the sulfonate is an alkyl-substituted benzene sulfonate, wherein the alkyl group has at least about 8 carbon atoms. 36. The composition of claim 35 wherein the aminophenol is an aminophenol of the formula: Where R ⁵ is a substantially saturated hydrocarbon-based substituent having an average of about 30 to about 400 aliphatic carbon atoms, R ⁶ is lower alkyl, lower alkoxy, nitro and halo. An element selected from the group consisting of; and z
Is 0 or 1. 37. The composition of claim 16 wherein said detergent / dispersant is (III) at least one hydrocarbyl substituted amine. 38. The composition of claim 37, wherein the amine is a monoamine of general formula AXNR ⁷ . 39. The composition of claim 37 wherein said hydrocarbyl substituted amine is a hydrocarbyl substituted aminohydrocarbyl morpholine of the general formula: embedded image Wherein R ⁷ is an aliphatic hydrocarbon group having about 30 to about 400 carbon atoms, A is hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or 1 to 10 A hydroxyhydrocarbyl group having a carbon atom, and U
Is an alkylene group having 2 to 10 carbon atoms. 40. The composition of claim 39 wherein said aminophenol is an aminophenol of the formula: Where R ⁹ is a substantially saturated hydrocarbon-based substituent having an average of about 30 to about 400 aliphatic carbon atoms, R ⁶ is lower alkyl, lower alkoxy, nitro and halo. An element selected from the group consisting of; and z
Is 0 or 1. 41. The detergent / dispersant is (I) at least 10
At least one acylated nitrogen-containing compound having a substituent having aliphatic carbon atoms, the compound comprising:
It is produced by reacting a carboxylic acid acylating agent with at least one amino compound containing at least one —NH group, wherein the acylating agent is an imide bond, an amide bond, an amidine bond or an acyloxyammonium bond. The compound is bound to the amino compound via
The composition of 6. 42. The composition of claim 41 wherein said amino compound is an alkylene polyamine of the general formula: embedded image Where U is an alkylene group having 2 to 10 carbon atoms; each R ⁸ is independently a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group, provided that at least one R 8 is ⁸ is a hydrogen atom, and n is 1-10. 43. The monocarboxylic acid or polycarboxylic acid, or an equivalent reactant thereof, containing an aliphatic hydrocarbyl substituent having at least about 30 carbon atoms. Composition. 44. The composition of claim 43, wherein the substituents are prepared from homopolymers or interpolymers of C _2-10 1-monoolefins or mixtures thereof. 45. The composition of claim 44, wherein said homopolymer or interpolymer is a homopolymer or interpolymer of ethylene, propylene, 1-butene, 2-butene, isobutene or mixtures thereof. 46. The composition of claim 45, wherein said aminophenol is an aminophenol of the formula: embedded image Where R ⁵ is, on average, a substantially saturated hydrocarbon-based substituent having from about 30 to about 400 aliphatic carbon atoms located in the ortho or para position of the hydroxyl group, R ⁶
Is an element selected from the group consisting of lower alkyl, lower alkoxy, nitro and halo; and z is 0 or 1. 47. The composition of claim 42, wherein the acylating agent is at least one monocarboxylic acid having 12 to 30 carbon atoms or their equivalent reactants. 48. The composition of claim 47, wherein the acylating agent is a mixture of fatty monocarboxylic acids or their equivalent reactants having straight or branched carbon chains. 49. An ethylene polyamine in which the amino compound has at least 2 up to about 8 amino groups,
Propylene polyamine or trimethylene polyamine,
Or a mixture of such polyamines.
Composition. 50. The composition of claim 49, wherein said aminophenol is an aminophenol of the formula: Where R ⁵ is a substantially saturated hydrocarbon-based substituent having an average of about 30 to about 400 aliphatic carbon atoms, R ⁶ is lower alkyl, lower alkoxyl, nitro and halo. Is an element selected from the group consisting of; and z is 0 or 1. 51. The detergent / dispersant is (IV) at least 1.
The composition according to claim 16, which is a nitrogen-containing condensate of a phenol compound, an aldehyde compound and an amino compound, each having -NH groups. 52. The composition of claim 51, wherein the phenol is an alkyl-substituted phenol and the alkyl group has at least about 30 carbon atoms. 53. The composition of claim 52, wherein the aldehyde is formaldehyde or their equivalent reactants. 54. The composition of claim 53, wherein said amino compound is an alkylene polyamine of the general formula: embedded image Where U is an alkylene group having 2 to 10 carbon atoms; each R ⁸ is independently a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group, provided that at least one R 8 is ⁸ is a hydrogen atom, and n is 1-10. 55. The condensate first reacts the phenol with the aldehyde in the presence of an alkali catalyst at temperatures up to 150 ° C., and then neutralizes the intermediate reaction mixture formed thereby. 55. The composition of claim 54, finally prepared by reacting the neutralized intermediate reaction mixture with at least one amino compound having at least one -NH group. 56. The composition of claim 51, wherein said aminophenol is an aminophenol of the formula: Where R ⁵ is a substantially saturated hydrocarbon-based substituent having an average of about 30 to about 400 aliphatic carbon atoms, R ⁶ is lower alkyl, lower alkoxyl, nitro and halo. Is an element selected from the group consisting of; and z is 0 or 1. 57. The composition of claim 55, wherein said aminophenol is an aminophenol of the formula: Where R ⁵ is a substantially saturated hydrocarbon-based substituent having an average of about 30 to about 400 aliphatic carbon atoms, R ⁶ is lower alkyl, lower alkoxyl, nitro and halo. Is an element selected from the group consisting of; and z is 0 or 1. 58. A composition comprising about 70 to 94 parts by weight of (A), about 5 to 18 parts by weight of (B) and about 1 to 12 parts by weight of (C).
Composition.