JPH0260996A - Hydroxyetheramine friction modifier for use in power transmission fluid, and wear-preventive additive used in combination therewith - Google Patents

Abstract

PURPOSE: To form a lubricant composite excellent in friction reforming characteristic and suitably used as an automatic transmission solution by blending a specified hydroxyetheramine compound to a mineral oil.

CONSTITUTION: The following components (a) and (b) are blended, whereby a lubricant composition suitably used as an automatic transmission solution is formed. (a) A mineral oil, and (b) a friction reforming quantity of a hydroxyetheramine compound having 10-30 boronated or non-boronated carbon atoms in total which is represented by formula I. In formula I, X is O or S; R₁ is a 3-27C saturated or unsaturated aliphatic hydrocarbon group; R₂ represents a straight or branched chain 1-6C alkylene group; R₃ is H or CH₃; R₄ and R₅ are independently a straight or branched chain 2-5C alkylene group. To the above composite, an organic phosphite represented by formula II may be blended in a quantity effective to impart wear resistance. In formula II, R₆ is an aryl or a 1-3C alkaryl, and R₇, R₈ are independently a 1-25C alkyl, an aryl, a 1-3C alkaryl, a 5-8C cycloalkyl or the like.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention encompasses fuel oils and lubricating oils, such as greases, industrial oils, gear oils, power transmission fluids, engine lubricating oils, especially automatic transmission fluids. The present invention relates to hydrocarbon soluble or dispersible and droxyetheramine friction modifying additives for oil-based compositions and oil-based compositions containing the same.

[Prior Art] As is well known, there are many cases where boundary lubrication conditions exist, particularly where two moving surfaces in contact with each other must be lubricated or protected to prevent wear and ensure continuous motion. do. There are other cases where the friction between two rubbing surfaces should be modified, but not necessarily minimized. By adjusting the friction between two surfaces, the power required to impart motion from one surface to the other is also adjusted.

For example, a particular property that should be imparted to certain lubricating oil compositions suitable for use as automatic transmission fluids is the friction-modifying properties of the fluid. This property is automatic transmission fluid (ATF)
distinguishes it from other lubricants and in fact also provides a distinction between ATF types. Characteristic qualities of this kind are transmission manufacturers and fluids +! ! It has received particular attention for many years by both manufacturers. This interest arises from the fact that the friction requirements of an ATF are unique and dependent on the transmission and clutch design and the type of clutch plate material used.

Another property that should be imparted to lubricating oil compositions, including automatic transmission fluids, is to reduce wear on, for example, bearings and power components.

As is also well known, both wear and friction modification can be adjusted by the addition of suitable additives, with varying degrees of success.

There are also many known additives that can be classified as antiwear or friction modifiers, but many of these additives are also known to behave differently physically or chemically and often compete with each other. , for example, they compete for the surfaces of moving metal parts that are subject to lubrication. Therefore, considerable care must be taken in selecting these additives to ensure compatibility and effectiveness.

Metal dihydrocarbyl dithiophosphates are one class of additives known to exhibit antioxidant and antiwear properties. The most commonly used additive of this type is zinc dialkyldithiophosphate (ZDDP), which is conventionally used in lubricant compositions. Although zinc compounds of this type provide excellent oxidation resistance and exhibit excellent wear resistance, they are corrosive.

Anti-wear agents and friction modifiers act by forming a coating on the surface of moving metal parts. Coating bonds are generally physically and/or chemically influenced. Therefore, if the bond between the antiwear agent and the metal part is stronger than the bond between the friction modifier and the metal part, the antiwear agent will Eliminate friction modifiers. The result is a loss of the friction modifier's ability to serve its intended purpose.

ATF friction and wear resistance is measured in various ways by vehicle manufacturers to evaluate the performance of additives with respect to specific transmission design requirements and their ability to impart transmission durability and smooth shifting in various road conditions. The test is designed.

Typically, friction modification is evaluated with a 5AENα2 friction device. In this test, the motor and flywheel of the friction device (filled with the liquid to be tested) are accelerated to a constant speed, the motor is stopped and the flywheel speed is reduced to zero by actuation of a clutch. The clutch plate is then released, the flywheel is again accelerated to constant speed, and the clutch pack immersed in the test fluid is re-engaged. This process is repeated many times, with each clutch engagement referred to as a cycle.

During clutch actuation, the friction torque is recorded as a function of time. The friction data obtained is either the torque trace itself or a friction coefficient calculated from this torque trace. The desired torque trace shape is set by the vehicle manufacturer.

One way to express this shape mathematically is to determine the torque when: (a) the flywheel speed is intermediate between the selected maximum constant speed and zero speed; Torque measurement is here referred to as TD), and (
b) When the flywheel speed reaches zero rpm (this torque measurement is T).

). Then, using these torques, T.

A torque ratio expressed as /To can be determined, or a torque difference expressed as To T□ can be determined. Optimal target values for torque ratios and torque differences are set by the vehicle manufacturer. T □ /
As T □ increases above 1, the transmission typically exhibits short and hard shifts when changing gears. On the other hand, when T □ /TD decreases below 1,
There is an increased risk that the clutch will slip when changing gears with the transmission. A similar relationship exists for the To-TD target value of zero.

Many automatic transmission fluids are T after a minimum number of cycles.

The target value of /H□ is achieved, but as the number of cycles increases, it becomes increasingly difficult to maintain this target value. The ability of the ATF to maintain this desired frictional property is referred to herein as frictional stability or durability. High levels of friction stability are difficult to achieve with ATF containing various antiwear additives.

As the ATF ages under the influence of frictional heat, it is believed that the antiwear agents are destroyed and the decomposition products displace the conventional friction modifiers at the metal/liquid lubrication interface. the result,
The liquids exhibit different frictional properties.

Attempts to improve friction stability by simply adding a friction modifier between the rows have not been successful. Because,
This is because it tends to reduce the liquid separation static pressure torque (Ts). Breakaway static pressure torque ratio (Ts/TD
), this parameter reflects the relative tendency of engagement parts such as clutch packs, bands and drums to slip under load. If this value is too low, slippage may occur, impairing the drivability and safety of the vehicle.

More recently, more stringent requirements regarding automatic transmission fluids have been set by one or more automobile manufacturers. The desire to improve fuel economy has led to reduced body and power drain sizes, smaller engines and higher shift speeds, and increased use of torque conversion clutches, sprag clutches, and shifts to front wheel drive.

Thus, transmission designs are undergoing rapid changes, thus requiring formulations of A King F additives that meet the new and more stringent property requirements necessary to accommodate these types of design changes.

Base oil alone cannot meet many of the special properties required for ATF use. Therefore, it is necessary to use several chemical additives, each designed to impart or enhance specific properties of the liquid. As a result, it would be particularly advantageous if one type of additive performed more than one function, reducing the number of additives that have to be present in the composition.

Accordingly, the search continues for new additives that have one or more properties suitable for use in ATF compositions as well as other oil-based compositions. Zarani, A.T.
Not only does it impart a variety of required specific properties to the F composition as well as other oil-based compositions, but it also reduces the effectiveness of various additives that interfere with the composition without showing a substantial tendency to compete with each other. New additive combinations are also being explored that are compatible with each other in the sense that they do not cause any damage. The present invention was developed in accordance with this research.

U.S. Pat. No. 2,290,880 discloses alcohol amine derivatives that can be used as interfacial modifiers in a variety of technologies. These compounds are said to be useful in lubricating oils and the like, allowing for the production of effective drilling, cutting, drilling, wire drawing, high-flex lubricants, and the like.

U.S. Pat. No. 3,255,253 discloses amine-containing polyols that are prepared by first cyanethylating an alcohol in the presence of a basic catalyst. The cyanoethylated alcohol is then hydrogenated to form a primary amine, which is then reacted with an alkylene oxide in the presence of a basic catalyst to form the desired amine-containing polyol. Amine-containing polyols are used in the production of polyurethane products, as curing agents for polyepoxy resins,
It is also said to be useful in the production of coatings and plasticizers.

U.S. Pat. No. 3,456,012 is directed to polyolefin adducts of T-alkoxypropylamine with surfactant properties.

U.S. Pat. No. 3,464,925 is directed to hydraulic fluids containing aminotriols.

Aminotriol is obtained by heating propylene oxide and triisopropylamine under pressure in the presence of an alkaline catalyst.

U.S. Pat. wherein A represents nitrogen, n represents an integer ranging from O to 100, and Z may represent hydrogen]. Alkyl sulfide compounds are disclosed to be antistatic agents.

U.S. Pat. No. 4,201,684 relates to a lubricating oil suitable for use as a crankcase lubricant in an internal combustion engine, comprising a friction-reducing amount of a sulfurized fatty acid amide, ester or ester-amide of an oxyalkylated amine. Contains.

US Patent No. 4,231,883@ relates to the use of alkoxylated hydrocarbyl amines in lubricating oils or fuels to reduce friction in internal combustion engines using the lubricating oils or fuels.

An example of an alkoxylated hydrocarbylamine compound disclosed in this US patent is N,N-bis(2-hydroxyethyl)oleylamine.

U.S. Pat. No. 4,486,324M discloses at least eight
Discloses an aqueous hydraulic fluid containing 0% water and containing hydrocarhylic-substituted succinic acid, zinc dihydrocargel dithiophosphate, hydroxyalkylamine, sodium alkylbenzene sulfonate, and optionally polyalkylene glycol heptanofatty acid ester. are doing.

U.S. Pat. No. 4,650,865 is directed to a method for making tertiary ether amines that do not exhibit surface active properties.

Tertiary ether amines can be used as surfactants and as starting materials for preparing surface-active derivatives such as amine oxides and quaternary ammonium compounds.

US Pat. No. 4,129,508 is directed to lubricant and fuel compositions featuring improved demulsification properties. This U.S. patent discloses the reaction product of a dialkyl phosphatide 1~, a polyisobutenyl-substituted anophosuccinic acid,
Commercially available tera-ethylenepentamine and U.S. Pat.
254,025 (lunar acid,
and a conventional friction modifier based on hishydroxyethyl tallow amino (Etomene T/12), the reaction product of polyisobutenyl succinic anhydride and ethylene polyamine, and a number of additives including Etomene C/15. Discloses a transmission fluid.

U.S. Pat. No. 2,151,300 discloses the use of a large proportion of mineral lubricating oil and a small proportion of organic phosphite, such as triphenyl phosphite, and a small amount of oil sufficient to provide substantial stability of the phosphorus compound. The present invention relates to a lubricating oil composition containing a soluble organic amine.

US Pat. No. 4,634,543 relates to fluid compositions for use in shock absorbers. The fluid composition consists of a lubricating base oil, a boron-containing compound, a phosphoric acid ester and/or a modified phosphoric acid ester (e.g., diphenylhydrogen phosphite 1~).

U.S. Pat.
A mixture of fatty acid esters of alkanolamines and hepano-, di-, or tri-organophosphite esters is added to the organic feed. Triorganophosphite esters include triphenylphosphite.

U.S. Pat. No. 3,484,375 discloses the production of additives for lubricating oils, intermediate distillate fuels, residual fuels or vacuum crude oils to improve their resistance to oxidation and sludge formation and to increase their viscosity index. or improve its flowability and pour point properties. These additives are produced by reacting organic phosphite esters with alkaline polyamines or amino alcohols. Suitable organic phosphite esters have at least one hydroxyl group attached to the phosphorus, but can also include triphenylphosphite.

U.S. Pat. No. 4,170,560 discloses an additive composition for use in crankcase lubricating oils, which consists of a mixture of an oil-soluble antioxidant and an oil-soluble hydroxylamine, the latter being an etomene and an oil-soluble hydroxylamine. (Sold by Almack Company, Inc., Aksina Division)

U.S. Pat. No. 4,529,528, for example, discloses reaction products of etomened dialkyl phosphites and boron compounds.

U.S. Pat. No. 4,382,006 discloses lubricating compositions containing friction-reducing amounts of boronated adducts of compounds including etomene.

U.S. Pat. No. 2,917,160 discloses the use of hydroxylated tertiary amines, including etomenes, as anticorrosion surface active lubricants for metal working. These amines can be used as salts. mM salt is exemplified.

U.S. Pat. No. 3,186,946 discloses cutting fluids in which the active lubricating component is a borate of a tertiary amine, including both etomenes and ethoduomenes.

U.S. Pat. No. 4,557,845 discloses the reaction product of etomene and di(C1-C6 hydrocarbyl) phosphite. This reaction product is about 80 to
temperature of 280 °C and about 5 to 100 of amine hydroxy groups
% reacts with the phosphite.

U.S. Pat. No. 3,509,052 relates to lubricating compositions containing a lubricating oil, a dispersant that is a derivative of substituted succinic acid, and a demulsifier. Although the demulsifier can be, for example, etomene, suitable demulsifiers are polyoxyalkylene polyols and their derivatives.

U.S. Pat. Produced by reaction with monocarboxylic acids. Phosphosulfurylated hydrocarbons are produced by reacting polymers of terpenes, petroleum flaxicone, or C2-C6A lefins with sulfides of phosphorus.

U.S. Pat. No. 2,805,217 is directed to condensation products of terpenes with phosphorus sesquisulfides and oxygen. These condensation products are used as antioxidants and detergents in lubricating oil compositions.

U.S. Pat. No. 3,511,780 discloses sludge dispersants,
The present invention relates to additives useful as antiwear agents, antioxidants, and inhibitors of harmful deposit formation in hydrocarbon compositions, including fuel oils and lubricants. This additive is
It is produced by condensing an alkenyl succinic anhydride with an aliphatic polyamine or with an aliphatic polyamine and a carboxylic acid, and then further condensing the condensation product with a polysulfurylated hydrocarbon and a dialkyldithiophosphoric acid. A suitable phosphosulfurylated hydrocarbon is exemplified by P2 S5-treated polyisobutylene.

U.S. Pat.
The additive package includes a dispersant, a phosphosulfurylated olefinic hydrocarbon, and a phosphorothionyl disulfide of phenol or 01-C18 alkylphenol.

- In a specific example, the dispersant is made by the reaction of polyisobutenyl succinic anhydride with tetraethylene pentamine, and the phosphosulfurylated olefinic hydrocarbon is made by the reaction of P2S5 with α-pinene, and the phosphosulfuryl Thionyl disulfide is derived from nonylphenol.

U.S. Pat. No. 4,557,845 discloses that the reaction product between 2-hydroxyethylalkylamine or a higher oxylated component and a dihydrocarbyl phosphite compound, or that a product of this type is used as a lubricant. It is disclosed that it is an effective friction modifier and fuel reduction additive for internal combustion engines when combined with liquid fuels. A similar disclosure is also found in U.S. Pat. No. 4,529.528,
In this case, the product is prepared by the reaction of a bis(2-hydroxyethyl)alkylamine, a hydride 1-cocarbyl phosphite, and a 1-mer compound.

U.S. Pat. No. 3,175,976 is directed to an automatic transmission fluid with improved high temperature stability. These fluids contain light oil in combination with di(↑-butyl)phenol, zinc dialkyldithiophosphate and alkyl methacrylate-vinylpyrrolidone copolymer.

U.S. Pat. No. 3,933,659 is directed to long-life functional fluids useful in automatic transmissions. The functional fluid of this U.S. patent comprises a principal amount of an oil of lubricating viscosity, an effective amount of an alkenyl succinimide, a Group H metal salt of dihydrocargyldithiophosphoric acid, and a basic sulfurized alkaline earth metal alkyl phenate; (a) (b) fatty acid amides of low molecular weight amino acids, (CAN-aliphatic alkyl-N, N-jetanolamine, (d>N -Aliphatic alkyl N, N-di(
(e) N-aliphatic-alkyl-N,N-di(polyquatoxy)ethanolamine, and (f) mixtures thereof.

U.S. Pat. No. 4,010,106 relates to a functional fluid useful in automatic transmissions, comprising an oil of lubricating viscosity and an effective amount of each of the following components: alkenylsuccinimide, dihydrocarbyl. A Group I metal salt of dithiophosphoric acid, a friction modifier, a basic sulfurized alkaline earth metal alkyl phosphate and containing about 15 to 50 carbon atoms and 20 to 60 weight percent chlorine and at least about 149 A chlorinated olefin with a boiling point of 300 °C. Friction modifiers that can be used in this functional fluid include fatty acid esters of polyhydric alcohols or oil-soluble oxyalkylated derivatives thereof, fatty acid amides of low molecular weight amino acids, N-aliphatic alkyl-N. Mention may be made of N-jetanolamine, N-fatty alkyl-N, N-di(ethoxyethanol)amine, N-fatty alkyl-N,N-di(polyethoxy)ethanolamine or mixtures thereof.

U.S. Pat. No. 4,208,293 discloses a lubricating oil composition suitable for use as a crankcase lubricant in internal combustion engines, containing a friction-reducing amount of a fatty acid amide or ester of jetanolamine. do. These compositions show improved results when containing zinc dihydrocargoldithiophosphate. Other additives may also be included in the composition, and among others mentioned in this patent are alkaline earth metal phenates and sulfurized phenates, alkaline earth metal hydrocarbyl sulfonates,
Phosphosulfurylated terpenes and polyolefins and their alkaline earth metal salts, poly-alkyl methacrylates or ethylene-propylene copolymers, ethylene-propylene non-conjugated terpolymers and 4,4-methylenebis-(2,6-di-t- butylphenol).

U.S. Pat. It is disclosed as a multifunctional additive for. These additives provide antioxidant, R2S control, corrosion protection and friction modifying properties.

U.S. Pat. No. 2,806,022 discloses neutralizing the reaction products of phosphorus sulfide and hydrocarbons with basic metal compounds. The neutralized product is used as a lubricating additive in the production of lubricants for internal combustion engines.

U.S. Pat. No. 2,316,080 relates to lubricants for internal combustion engines, such as automobiles and diesel engines, under severe conditions to prevent corrosion, piston ring sticking, cylinder wear and carbon and or) varnish formation can be addressed. These lubricants consist of a lubricating oil and the reaction product of neutralized or partially neutralized phosphorus sulfide and a monoolefin hydrocarbon polymer. The neutralized or partially neutralized products, or metal derivatives thereof, can be used alone or in combination with unneutralized sulfurized phosphorus-olefin polymer reaction products in lubricating oils. Neutralization of the phosphorus sulfide-olefin polymer reaction product is carried out by adding to this reaction product a suitable alkaline compound such as an alkali or alkaline earth metal hydroxide, carbonate or oxide, preferably potassium hydroxide. You can do it by doing this.

Ammonia or alkyl or aryl substituted amines can also be used. Similar disclosures can be found in US Pat. No. 2,316,082 and US Pat. No. 2,316,088.

U.S. Pat. No. 3,034,907 discloses compositions of materials effective to inhibit or inhibit rust formation on iron surfaces and ice formation in the intake system of internal combustion engines. The composition is characterized in that it contains (a) a hydrophobic organic carrier, (b) a carboxylic acid amide monocarboxylic acid, and (C) at least an equivalent amount of a hydroxyalkylated nitrogen base having at least one lipophilic group. The hydroxyalkylated nitrogen base has the general formula: [wherein L represents the above-mentioned lipophilic group, and X is bonded to the nitrogen atom by an aliphatic carbon atom, and
-8-alkylene, -0-hydroxyalkylene, -8
-hydroxyalkylene and R'N-alkylene (where R' = H1 low molecular weight alkyl or low molecular weight hydroxyalkyl, -CO-O-alkylene and -
represents a crosslinking group selected from the group consisting of C0-0-hydroxyalkylene group]. In the above formula, n represents O or 1, R1 represents hydrogen, lower alkyl, lower hydroxyalkyl, or lower aminoalkyl group, and R2 represents (
L-X, ) and R1. In all cases, the group X,
At least one of R1 and R2 is a lower hydroxyalkylated aliphatic group.

U.S. Pat. No. 3,235,501 is directed to an oil composition containing a foam-promoting detergent, a silicone polymer anti-foam agent, and a small amount of a foam-blocking polyalkyloxylated aliphatic amine. The polyalkyloxylated aliphatic amines correspond to one of the following formulas "a" or "b", depending on whether the amine from which they are made is a monoamine or a diamine: where R is from about 4 to an aliphatic group having about 24 carbon atoms, -R'0- is an alkylene oxide group selected from the group consisting of ethylene oxide and propylene oxide;
n is an integer from 1 to about 25, and X is hydrogen, R and -
(R'0)2H groups, in all cases the combined number of the parentheses is 25 or less; and: where RII is an aliphatic group having from 2 to about 6 carbon atoms; and R'O, n and X are as described for formula "a", but at least one ] The detergent disclosed in this US patent has a high molecular weight (300
~1000) oil-soluble total salts of sulfonic acids, such as petroleum-derived sulfonic acids and synthetic alkyl-aryl sulfonic acids having from about 8 to about 24 carbon atoms in the alkyl moiety;
Neutral or basic (complex or overbased) barium and calcium sulfonates, metal salts of alkylphenol sulfides, such as neutral or basic (complex) barium and calcium salts of amyl- and nonyl-substituted phenol sulfides; Metal salts of phosphorus sulfide-hydrocarbon reaction products are present. Particular salts having this property are metal salts of phosphosulfurylated polyolefins, such as the barium salt of the P2S5-polypropylene reaction product. This kind of salts is, for example, the above-mentioned US Pat.
No. 16.080, No. 2.316,082, No. 2,31
6,088 and 2,806,022.

U.S. Pat. No. 4,664,826M relates to metal salt esters of didrocarbyl-substituted succinic acids or anhydrides (e.g. octadecylsuccinic anhydride) and alkanols (e.g. diobis-ethanol), which include, for example It can exhibit friction-modifying properties, anti-oxidation properties, and anti-corrosion properties in power transmission fluids such as moving transmission fluids.

U.S. Pat.
C1-C20) human 1]carbyl group, 1<' and R'' are 211IIi(C1-C1o) alkylene groups, a is an integer from about 1 to about 10, and x+y is about 1
A dialkoxylated alkylpolyoxyalkylamine having a numerical value of ~20] is included as a polishing modifier.

SUMMARY OF THE INVENTION The present invention is based on the discovery that certain hydroxyetheramine compounds have friction-modifying properties and are compatible with other conventional additives. The hydroxyetheramine friction modifiers of the present invention are stable and therefore do not adversely affect the friction stability of fuels and lubricants containing them. In summary, the hydroxyetheramine friction modifiers of the present invention have been found to be desirable additives for use in oil-based compositions, particularly power transmission fluids, and more particularly automatic transmission fluids.

In one aspect of the invention, the formula: [wherein R1 represents a 03-C27 saturated or unsaturated aliphatic hydrocarbon group, and R2 represents a linear or branched C1-
Represents a C6 alkylene group, R3 is )-1 or CH3
and R4 and R5 are independently the same or different linear or branched fullkylene groups (preferably linear alkylene), about C2 to about C5, preferably C2
alkylene, p and p' independently represent 1 to 4, preferably 1 to 3 (e.g. 1), X represents O or S, and preferably a total of about 10 to about 3
0 carbon atoms present] A hydroxyetheramine compound friction modifier is provided.

The above-mentioned hydroxyetheramine additives, when combined with other conventional additives, provide excellent wear resistance, static and dynamic friction coefficients, friction modification and stability, dispersibility, sludge inhibition, antioxidant properties and resistance. Strict A in terms of proper balance of corrosivity
Particularly suitable for meeting TF requirements.

In other aspects of the invention, the above and droxyether amine friction modifying compounds may be used in combination with l-lyarylphosphite wear inhibitors such as triphenylphosphite 1-1.

In another aspect of the invention, the hydroxyetheramine friction modifying compound can be used as the boronation reaction product of the hydroxyetheramine compound and a boron compound, such as boric acid or a C1-C4 trialkylborate. .

In another aspect of the invention, an oil-based composition comprising an oil-based material selected from the group consisting of fuels and lubricating oils and at least one boronated or non-boronated hydroxyetheramine friction modifying compound. is provided.

In accordance with another practical fM aspect of the present invention, at least 1
There is provided a lubricating oil composition suitable for use as an automatic transmission fluid comprising the above-described hydroxyetheramine friction modifying additives of the types described above.

According to another embodiment of the present invention, there is provided a lubricating oil composition suitable for use as a power transmission fluid comprising a lubricating oil in which at least one of the above-described hydroxyetheramine compounds is dissolved or dispersed.

According to another embodiment, the lubricating oil is suitable for use as a power transmission fluid, comprising a lubricating oil in which at least one of the above-described hydroxyetheramine compounds and a triarylphosphite anti-wear additive are dissolved or dispersed. A lubricating oil composition is provided.

According to another aspect of the present invention, a method is provided for improving the static and dynamic coefficient of friction and frictional stability of a lubricating oil composition suitable for use as a power transmission fluid, the method is characterized in that at least one of the above hydroxyetheramine compounds is added to the lubricating oil composition.

The hydroxyetheramine friction modifying additive of the present invention comprises:
The following structural formula: where R1 is a straight or branched chain saturated or unsaturated aliphatic hydrocarbon group (preferably straight chain alkylene), typically from about C3 to about C27, preferably from about C+o to Approximately 0
20, particularly preferably about C+o-C1e, R2 is a straight-chain or branched alkylene group (preferably straight-chain alkylene), in the negative form 02 to about 06, preferably about 02 to about C4 , particularly preferably represents C3 alkylene, R3 represents H or CH3, preferably H, and R4 and R5 may be the same or different and independently represent a straight-chain or branched alkylene group (preferably straight-chain alkylene). ), typically about C2 to about C5, preferably C2
represents alkylene, and p and p' are independently 1-4,
preferably represents 1 to 3, and X represents O or S, preferably represents O]. In a particularly preferred embodiment, X represents O, R1 and R3 have a total of 18 carbon atoms, R2 represents C3 alkylene, and R4 and R5 each represent C2 alkylene. In all cases,
The total number of hydroxyetheramine compounds is from about 10 to about 3
Preferably it has 0 carbon atoms.

When
Here, the alkanol is first reacted with an unsaturated nitrile, such as acrylonitrile, in the presence of an initiator to form an ethernitrile intermediate. This intermediate is then hydrogenated to form the ether amine, preferably in the presence of a conventional hydrogenation catalyst such as Nanney Nickel.

The ether amine is then reacted with an alkylene oxide, such as ethylene oxide, in the presence of an alkaline catalyst in a conventional manner at a temperature in the range of about 90 DEG to 150 DEG C. The overall process for preparing the desired hydroxyetheramine compounds is described, for example, in U.S. Pat. No. 3,255,253 and can be illustrated by the following formula: Formula 1 Formula 2 Formula 3 R and R' represent straight-chain or branched alkyl groups.
They can be prepared by conventional free radical reactions between hydroxyalkyl mercaptans, such as hydroxynityl mercaptan, to form long chain alkylhydroxyalkyl sulfides. The long chain alkyl hydroxyfurkyl sulfide is then mixed with thionyl chloride at low temperature and then heated to about 40°C to form the long chain alkyl chloroalkyl sulfide.

The long chain alkylchloroalkyl sulfide is then reacted with a dialkanolamine, such as jetanolamine, and with an alkylene oxide, such as ethylene oxide, optionally in the presence of an alkaline catalyst and at a temperature of about 100°C. The reaction yields the desired hydroxyetheramine compound. Methods of the above type are known in the art and are disclosed, for example, in U.S. Patent No. 3,705,1.
No. 39, the disclosure of which is cited here for reference.

The hydroxyetheramine compound can be used as is. However, they cannot be used as adducts or reaction products with chemical compounds such as, for example, boron oxide and metaphorates, fatty acids or heptano-, di- or tri-hydroxycarbyl (e.g. 1-realkyl) borays. You can also do it.

Adducts or derivatives of this type can be represented, for example, by the following structural formula: where R1, R2, R3, R4, R5, p and p' have the same meanings as above, and R' is H or an alkyl group.

Representative examples of alkyl borates that can be used to monopolinate alkyl amine compounds include mono-, di-, and tributyl borates, and hepnotic, di-, and trihexyl borates, and the like. The boronated adak 1- is prepared by simply heating the mixture of the hydroxyetheramine compound and the boron compound at about 100'C, preferably in the presence of a suitable solvent.
The boronization level may be, for example, from about 1.0 to about 5.0.
It can vary widely over a range of weight percentages.

Boriding methods of this type are well known in the art, and include, for example, U.S. Pat.
No. 1 and No. 4.38.2,006, the disclosures of which are hereby incorporated by reference.

As mentioned above, the hydroxyetheramine friction modifiers of the present invention are particularly suitable for use in oil-based compositions containing organophosphite esters as antiwear additives. Organic bosphite esters that can be used are of the formula: where R6 is a hydrocarbyl group selected from the group consisting of aryl and C1-C3 alkaryl;
and R8 are characterized by the same or different hydrocarbyls selected from the group consisting of C1-C25, preferably C6-C20, particularly preferably C8-C18 alkyl, C1-C3 alkaryl and their octo-substituted derivatives. can do.

Representative examples of suitable R6, R7 and R8 groups of formula (1) include octyl, nonyl, decyl, dodecyl, hexyl, octadecyl and phenyl, with phenyl being preferred.

In most cases it is preferred that Re, R7 and R8 are the same.

Organic bosphite esters can be obtained by direct esterification of phosphoric acid or phosphorus trihalide with phenol or alcohol or mixtures thereof. Methods for producing organic bosphite Nisdel are conventionally known and are described, for example, in US Pat. No. 3,513,093, the disclosure of which is incorporated herein by reference.

The mixture of organophosphite ester and hydroxyetheramine compound in the present invention has been found to have multifunctional properties including wear resistance, abrasion modification, friction stability, and copper corrosion resistance.

Hydroxyether amine friction modifying compounds are therefore preferably combined with organophosphite ester compounds to be incorporated into and dissolved or dissolved in oily substances such as fuels and lubricating oils, especially power transmission fluids such as automatic transmission fluids. Used in a distributed manner.

The combination of the hydroxyetheramine compound or the organic phosphite ester compound and the hydroxyetheramine compound of the present invention can be used, for example, in kerosene, diesel fuel,
Household heating fuel oil, jet fuel, etc. approximately 66°C (1
DI! Approximately 0.1 to approximately 1% by weight in terms of type
Concentrations of organic bosphite additives in the fuel in the range of 0.2% to about 0.8% by weight, particularly preferably 0.3% to about 0.6% by weight are generally used. Similarly,
In terms of shape, it is about 0.05 to about 5 pp based on the total weight of the composition.
A concentration of the hydroxyetheramine compound addition^1] is used, preferably in the range from 0.08 ppm to about ippm, particularly preferably from 1 to about 0.5 ppm.

However, the additive combination according to the present invention has its primary use in lubricating oil compositions using a base oil in which the additives are dissolved or dispersed.

Base oils of this type may be natural or synthetic, with greater advantages being provided by natural base oils.

For example, base oils suitable for use in making the lubricating compositions of the present invention include crankcase oils for spark-ignited and compression-ignited internal combustion engines, such as automotive and i-rack engines, underwater and railroad diesel engines, etc. Includes those conventionally used as lubricating oils. The additive combination of the present invention is particularly useful when used in base oils conventionally used in power transmission fluids, such as automatic transmission fluids, tractor fluids, universal tractor fluids and hydraulic fluids, heavy hydraulic fluids, power steering fluids, etc. A favorable result is obtained. Gear lubricants, industrial oils, pump oils and other lubricating oil compositions may also benefit from incorporating the additives of the present invention.

For example, the additives of the invention are preferably incorporated into synthetic base oils such as dicarboxylic acids, polyglycols and alcohol alkylnisdales; polyalpha-olefins, alkylnisdales, organic esters of phosphoric acids, polysilicone oils, etc. be able to.

Naturally based oils are classified according to their composition (depending on whether they are paraffinic, naphthenic, mixed paraffin-nastenic, etc.) and their production, e.g. distillation range, straight run or pyrolysis, hydrofluoric acid, etc. mineral lubricating oils that vary widely (depending on inning, solvent extraction, etc.).

More particularly, the natural lubricating oil basestocks that may be used in the compositions of the present invention may be straight run mineral lubricating oils or distillates derived from paraffinic, naphthenic, bituminous or mixed base crude oil systems. Alternatively, if desired, various blended oils and residual oils, especially those from which asphalt components have been removed, can be used. The oil can be purified with acids, alkalis and/or other substances such as aluminum chloride, or with other substances such as phenol, sulfur dioxide, furfural, dichlorodiethyl needle, nitrobenzene, chlorine aldehyde. It can also be an extracted oil produced by solvent extraction using a solvent such as.

The lubricating oil base stock conveniently has a concentration of typically about 2.5 to about 12, preferably about 3.5 to about 9C5t at 100°C.
It has a viscosity of

The additives of the present invention can be used in lubricating oil compositions, typically consisting of a large amount of lubricating oil and typically a small amount of additive, to provide improved friction modification over that in the absence of the additive. It is effective in imparting quality, abrasion resistance, and abrasion stability. Other conventional additives selected to meet the particular requirements of the selected type of lubricating oil composition may also be included, if desired.

The additives of the present invention are oil-soluble, ie soluble in oil, or stably dispersed in oil, with suitable solvents. The terms oil-soluble, soluble, or stable dispersion, as used herein, do not necessarily indicate that these substances are soluble, soluble, miscible, or suspended in the oil in all proportions. do not have. However, this means that each additive is soluble or stably dispersible in the oil to a sufficient degree to exert its intended effect in the oil environment. Additionally, the optional incorporation of other dispersants and/or other additives allows for the incorporation of higher levels of certain organophosphite ester or hydroxyether amine compounds.

The additives of this invention can be incorporated into lubricating oils in any convenient manner. For example, they can be added directly to the oil by being dispersed or dissolved in the oil at the desired level of concentration, typically in a suitable solvent such as mineral oil.

This type of formulation can be carried out at room temperature or elevated temperature. Alternatively, the combination of organophosphimyl ester and hydroxyether amine additive can be combined with a suitable oil-soluble solvent and base oil to form a concentrate, and this concentrate can then be combined with a lubricant base stock to form the final composition. You can also get things.

The lubricant base stock for the additives of the present invention is typically adapted to perform a selected function by incorporating the additive therein to form a lubricating oil composition.

As mentioned above, a wide variety of lubricating oil compositions suitable for use in combination with the additives of the present invention include power steering fluids, tractor fluids, 10,000 nK tractor oils, and the like.

The advantages of the additive according to the invention are particularly pronounced when used in lubricating oils suitable for use as automatic transmission fluids.

Power transmission fluids, such as automatic transmission fluids, and lubricating oils in general are typically formulated from a number of additives that are useful to enhance their chemical and/or physical properties, respectively. These additives are generally sold as concentrate packages in which mineral oil or other base oil is present. Mineral lubricating oils in automatic transmission fluids are typically refined hydrocarbon oils or mixtures of produced hydrocarbon oils selected depending on the viscosity requirements of the particular fluid! 11! Typical viscosity ranges from 2.5 to 9, for example from 3.5 to 9, at 100°C. Suitable base oils include a wide variety of light hydrocarbon mineral oils, such as naphthenic base oils, paraffinic base oils and mixtures thereof.

Typical additives typically present in this type of package as well as in the final composition are viscosity index (V, 1.) improvers, corrosion inhibitors, antioxidant β1j, friction agents, lubricant flow improvers, dispersants. , anti-foaming agents, anti-wear agents, detergents, metal rust inhibitors and seal swelling JVI agents.

Viscosity modifiers provide high and low temperature operating properties to lubricating oils, as well as providing shear stability at high temperatures and acceptable viscosity or flow properties at moderately low temperatures.

The v, r, improver is generally a high molecular weight hydrocarbon polymer, more preferably a polyester. Zarani, V, 1. Enhancers can also be derivatized to include other properties or functions, such as adding dispersion properties.

These oil-soluble V, 1. Polymers generally have a molecular weight of 103 to
106, preferably 104-106, for example 20.0
It has a number average molecular weight of 00 to 250.000.

Examples of suitable hydrocarbon polymers are C2-C30 (e.g. 0
2~Co) Two or more monomers of olefins (linear or branched aliphatic, aromatic, alkyl-
It includes homopolymers and copolymers of α-olefins and internal olefins (which can be aromatic, cycloaliphatic, etc.). Often these are ethylene and C3-C3
The copolymer is a copolymer with zero olefin, particularly preferably a copolymer with ethylene and propylene. For example, polyisobutylene, homopolymers and copolymers of C6 and higher α-olefins, atactic polypropylene, hydrogenated polymers, and copolymers and terpolymers of styrene with, for example, isoprene and/or butadiene. Other polymers such as polymers can also be used.

More specifically, other hydrogen polymers suitable as viscosity index improvers in the present invention include conjugated dienes and/or monovinyl aromatic compounds and optionally α-olefins or lower alkenes (e.g. C3-CI(lα- as hydrogenated or partially hydrogenated homopolymers and random, Cheebird, star or block copolymers (including terpolymers, quaternary polymers, etc.) with olefins or lower alkenes); Conjugated dienes include isoprene, butadiene, 2,3-dimethylbutadiene, piperylene and/or mixtures thereof, such as mixtures of isoprene and butadiene. Monovinyl aromatic compounds include vinylodines or polystyrene. - including aromatic compounds (e.g. vinylnaphthalene) or mixtures of vinyl-naphthalene and/or poly-aromatic compounds, but preferably monoaromatic compounds, e.g. styrene or in which the α-carbon atom of styrene is substituted; Alkylated styrenes, such as α-methylstyrene, or alkylated styrenes substituted on ring carbons, such as 0-1m-1p-methylstyrene, ethylstyrene, propylstyrene, isopropylstyrene, butylstyrene, isogylstyrene, t -butylstyrene (e.g. pt-butylstyrene).Also includes vinylxylene, methylethylstyrene and ethylvinylstyrene.α-olefins and lower Alkenes preferably include ethylene, propylene, azone, ethylene-propylene copolymers, isobutylene and polymers and copolymers thereof. The lock copolymers contain relatively small amounts (i.e., less than about 5 mole percent) of other copolymerizable heptamers, such as vinylpyridine, vinyllactams, methacrylates, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl stearate, etc. can be included.

Specific examples include random polymers of butadiene and/or isoprene and polymers of isoprene and/or butadiene with styrene. Typical block copolymers include polystyrene-polyisoprene, polystyrene-polybutadiene, polystyrene-polyethylene, polystyrene-ethylene propylene copolymers, polyvinylcyclohexane-hydrogenated polyisoprene, and polyvinylcyclohexane-hydrogenated polybutadiene. Cheebird polymers include polymers of the above monomers made by methods known in the art. Star polymers typically consist of a core and polymeric arms attached to the core, the arms being composed of the conjugated diene and/or monovinyl aromatic unsaturated homopolymer or copolymer. . Typically, at least about 80% aliphatic unsaturation and about 20% aromatic unsaturation in the star polymer is reduced by hydrogenation;
be done.

Representative patents disclosing hydrogenated polymers or copolymers of this type are U.S. Pat.
No. 18.813, No. 3.630.905, No. 3,66
No. 8,125, No. 3.763,044, No. 3.795
, No. 615, No. 3,835,053, No. 3,838,
No. 049, No. 3,965,019, No. 4, 358.5
No. 65@ and No. 11,557,849, the disclosures of which are hereby incorporated by reference.

The polymer can have its molecular weight reduced, for example by kneading, extrusion, oxidation or thermal degradation, and can also be oxidized or contain oxygen. Derivatized polymers such as post-grafted copolymers of ethylene-propylene and active monomers, such as maleic anhydride, which can react with further alcohols or amines (e.g. alkylene polyamines or hydroxyamines) (e.g. U.S. Pat. 4.089,791!, 4.160.739, 4.137.185) or copolymers of ethylene and propylene reacted with or grafted with nitrogen compounds, e.g. Patent cylinder 4.068.0
No. 56, No. 4.068,058, No. 4.146.48
9 and 4.149.984) are also included.

Suitable hydrocarbon polymers include 15-90% by weight of ethylene (
Preferably 30-80% by weight of ethylene) and 10-85% by weight
% by weight (preferably 20 to 70% by weight) of one or more α-olefins of 03 to 028, preferably C3 to C1θ, more preferably 03 to C8. . Although not required, such copolymers preferably have a crystallinity of less than 25% by weight as determined by X-ray and differential scanning calorimetry. Particularly preferred is the copolymerization of ethylene and propylene. Other α-olefins suitable for use in place of propylene to form copolymers or in combination with ethylene and propylene to form terpolymers, quaternary polymers, etc. are 1-butene, 1- Includes pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. For example, 4-methyl-1-pentene,
4-methyl-1-hexene, 5-methylpentene-1,
Branched α-olefins such as 4,4-dimethyl-1-pentene and 6-methyl-heptene-1, and mixtures thereof are also suitable.

A terpolymer or a quaternary polymer of ethylene, the C3-28 α-olefin, a non-conjugated diolefin, or a mixture of these diolefins can also be used. The amount of non-conjugated diolefin generally ranges from about 0.5 to 20 mole percent, preferably from about O to about Y mole percent, based on the total amount of ethylene and alpha-olefin present.

Preferred V, 1. The improver is a polyester, particularly preferably an ethylenically unsaturated C3-C polyester, such as methacrylic acid and acrylic acid, maleic acid, maleic anhydride, fumaric acid, etc.
8 mono- and di-carboxylic acids.

Examples of unsaturated esters that can be used are esters of aliphatic saturated monoalcohols having at least 1 carbon atom, preferably 12 to 20 carbon atoms, such as decyl acrylate, lauryl methacrylate, cetyl methacrylate. , stearyl methacrylate, and mixtures thereof.

Other esters include vinyl alcohol esters of C2-C22 fatty acids or monocarboxylic acids, preferably saturated vinyl acetate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, and the like, as well as mixtures thereof.

Copolymers of vinyl alcohol esters and unsaturated acid esters, such as vinyl acetate and dialkyl fumarate, can also be used.

The ester is an unsaturated monomer, e.g., per mole of unsaturated ester or unsaturated acid or anhydride.
copolymerized with 0.2 to 5 moles per El of an unsaturated monomer such as a C2-C20 aliphatic or aromatic olefin;
Subsequent esterification can also be carried out. For example, copolymers of maleic anhydride and styrene esterified with alcohols and amines are known (see, for example, US Pat. No. 3,702,300).

This type of ester polymer can be grafted with or copolymerized with polymerizable unsaturated nitrogen-containing monomers to form V, 1. It is also possible to impart dispersibility to the improver. Examples of suitable unsaturated nitrogen-containing monomers for imparting dispersibility are those containing 4 to 20 carbon atoms, such as amine-substituted olefins such as p-(β-diethylamineethyl)styrene; polymerizable Basic nitrogen-containing heterocyclic compounds with ethylenically unsaturated substituents, such as vinylpyridine and vinylalkylpyridine, such as 2-
Vinyl-5-ethylpyridine, 2-methyl-5-vinylpyridine, 2-vinyl-pyridine, 3-vinyl-pyridine, 4-gonyl-pyridine, 3-methyl-5-vinyl-
Pyridine, 4-methyl-2-vinyl-pyridine, 4-ethyl-2-vinyl-pyridine, 2-butyl-5-vinylpyridine, and the like.

N-vinyl lactams, such as N-vinylpyrrolidone or N-vinylpiperidone, are also suitable.

Vinylpyrrolidone is preferred and N-vinyl-pyrrolidone, N-(1-methyl-vinyl)pyrrolidone, N-
Vinyl-5-methyl-pyrrolidone, N-vinyl-3,3
-dimethylpyrrolidone, N-vinyl-5-ethylpyrrolidone, and the like.

Corrosion inhibitors, also known as corrosion inhibitors, reduce the deterioration of non-ferrous metal parts that come into contact with liquids.

Examples of corrosion inhibitors include phosphosulfurylated hydrocarbons and phosphosulfurylated hydrocarbons and alkaline earth metal oxides or hydroxides, preferably in the presence of alkylated phenols or alkylphenone thioethers and preferably of carbon dioxide. It is a product obtained by reacting in the presence of As mentioned above, phosphosulfurylated hydrocarbons include a suitable hydrocarbon, such as a terpene, a heavy oil fraction of a Z02-C6 olefin polymer, such as polyisobutylene, and 5 to 30% by weight of phosphorus sulfide. 66°C (1
It is produced by reacting at a temperature ranging from 50° C. to 204° C. (400° C.). Neutralization of phosphosulfurylated hydrocarbons can be carried out as taught in U.S. Pat. No. 2,969,324.

Other suitable corrosion inhibitors are hydrocarbyl-thio-disubstituted derivatives of '1.3.4-thiadiazole (e.g. C2
~C3o); Includes copper corrosion inhibitors consisting of alkyl, aryl, cycloalkyl mono-, di-1-ri-1- or thio-bicyclic derivatives.

A typical example of this type of substance is 2.5-bis (Okujiruchi 1
1,3,4-deadiazole; 2,5-thiadiazole; 2,5-bis(
Octyl trithi A) 1,3,4-thiadiazole; 2,
5-His(octyltetrathio)-1.3.4-thiadiazole; 2,5-bis(nonylthio)-1.3.4-
Deadiazole; 2,5-bis(dodecyldithio)-1
．． 3,4-thiadiazole; 2,5-bis(cyclohexyldithio)-1.3.4-thiadiazole; 2-dodecyldithio-5-phenyldithio-1.3.4-thiadiazole; and mixtures thereof.

Suitable copper corrosion inhibitors are derivatives of 1,3,4-thiadiazole [e.g., U.S. Pat. No. 2,719,12
No. 5, No. 2, 719, 126 and No. 3, 087
, No. 932]. Particularly preferred is the compound 2,5-bis(t-ocdyldio)-1.3.

4-thiadiazole [commercially available as Amoco 150], and 2,5-bis(1-nonyldithio) 1,3.
4-thiadiazole [commercially available as Amoco 158].

The manufacture of this type of material is also covered by U.S. Patent No. 2,719,12.
No. 5, No. 2, 719, 126, No. 3, 087,
No. 932M and 4,410,436, the disclosures of which are hereby incorporated by reference.

Oxidation inhibitors reduce the tendency of mineral oils to deteriorate during use;
This deterioration is evidenced by oxidation products such as sludge and varnish-like deposits on metal surfaces. Oxidation inhibitors of this type are preferably alkaline earth metal salts of alkylphenol thio-[-del with 05-C12 alkyl side chains, such as calcium nonylphenol sulfide,
Includes barium mono-octylphenol sulfide: arylamines such as dioctyl phenylamine, ) 12-alpha naphthylamine; phosphosulfurylated or sulfurylated hydrocarbons, and the like.

The friction modifier acts to impart appropriate friction properties to A 1-F as required by the automotive industry.

In the present invention, the hydrotetraamine compound functions as the primary friction modifier.

Dispersants maintain oil insolubles resulting from oxidation in suspension in the liquid during use and prevent flocculation and settling of the sludge. Suitable dispersants include, for example, ash-forming or ashless dispersants, with the latter being preferred.

Ash-forming dispersants are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids or organophosphoric acids, which are exemplified by olefin polymers, e.g. (polyisobutyne) with a phosphorylating agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and sulfur halide or chlorophosphorothionyl chloride. characterized by a direct carbon-phosphorus bond. The most commonly used salts of this type of acid are the sodium, potassium, lithium, calcium, magnesium, strontium and barium salts.

The term "basic salt" is used to mean a metal salt in which the metal is present in stoichiometrically greater amount than the organic acid groups.

The most commonly used method for preparing basic salts is to add a solution of the acid in mineral oil to a stoichiometric excess of a metal, such as a metal oxide, hydroxide, carbonate, bicarbonate or sulfide. It consists of heating at a temperature of about 50° C. with a powder and filtering the material obtained. It is also known to use "accelerators" in the neutralization step to promote the incorporation of large excess metals. Examples of compounds useful as accelerators are phenolic substances such as phenol, naphthol, alkylphenols, thiophenols, sulfurized alkylphenols and condensation products of formaldehyde and phenolic substances; for example methanol, 2-propanol, octyl alcohol, Alcohols such as cellosolve, ethylene glycol, stearyl alcohol and cyclohexyl alcohol; and amines such as aniline, phenylene diamine, phenyl-β-naphthylamine and dodecylamine. A particularly effective method for preparing these basic salts consists of mixing the acid with an excess of a basic alkaline earth metal neutralizer and at least one alcohol promoter and heating the mixture at a temperature of e.g.
It consists of carbonization at elevated temperatures. This type of substance has been described above with respect to detergents and metal rust inhibitors.

The most preferred ash-forming detergents include metal salts of sulfonic acids, archimephenols, sulfurized alkylphenols, alkylsalicylic acids, naphthenic acids and other oil-soluble mono- and dicarboxylic acids. Highly basic (i.e. overbased)
Metal salts, such as highly basic alkaline earth metal sulfonates (particularly Ca and MCI salts), are often used as detergents.

These generally involve heating a mixture of oil-soluble or alkaryl sulfonic acids with an alkaline earth metal compound in excess of that required for complete neutralization of the sulfonic acids present, and then removing the excess metal. It is produced by forming a dispersed carbonate complex by reaction with carbon dioxide to produce the desired overbased character. Sulfonic acids are commonly used in the sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from petroleum fractions by distillation or extraction.
Alternatively, they may be obtained by alkylation of aromatic hydrocarbons, such as those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl and halogen derivatives (eg chlorobenzene, chlorotoluene and chlornaphthalene). Alkylation is carried out in the presence of a catalyst by 3
It can be carried out using alkylating agents having up to 30 carbon atoms or more (for example, helobarafine, olefins which are prepared by dehydrogenation of paraffins, polyolefins such as polymers from ethylene, propylene, etc.). Generally, the alkaryl sulfonates contain from about 9 to about 70 or more carbon atoms, preferably from about 16 to about 50 carbon atoms per alkyl-substituted aromatic acid moiety.

Alkaline earth metal compounds that can be used to neutralize these alkaryl sulfonic acids to form sulfonates include oxides and hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydroxides of magnesium, calcium, and barium. Includes sulfides, nitrates, borates and ethers. Examples are calcium oxide, calcium hydroxide,
Magnesium acetate and magnesium borate. As mentioned above, the alkaline earth metal compound is used in excess of that required for complete neutralization of the alkaryl sulfonic acid. Generally, this collapse will be from about 100% to about 220% of the stoichiometric amount of metal required for complete neutralization, but at least 1%
Preferably, 25% is used.

Various other methods of making basic alkaline earth metal alkaryl sulfonates are known and are described, for example, in U.S. Pat. Nos. 3,150,088 and 3,150,089, in which The properties are obtained by hydrolysis of alkoxide-carbonate complexes with alkaryl sulfonates in hydrocarbon solvents/diluent oils.

Ashless dispersants are suitable dispersants for use in connection with the present invention, despite the fact that, depending on their composition, the dispersants produce non-volatile substances on combustion, such as boron oxide or phosphorus pentoxide. It is said that However, they generally do not contain metals and therefore do not produce metal-containing ash upon combustion. Many types of ashless dispersants are known in the art, some of which are suitable for use in the lubricant compositions of the present invention. Examples are: (1) at least about 30, preferably at least about 5
carboxylic acid having 0 carbon atoms or its derivative)
and nitrogen-containing compounds such as amines, hydroxy compounds such as phenols and alcohols, and/or basic inorganic substances. these"
Examples of "carboxylic acid dispersants" include British Patent No. 1.3.
No. 06.529, as well as U.S. Patent No. 3.272.746.
No. 3,341,542, No. 3,454,607, and No. 4,654,403.

More particularly, nitrogen- or ester-containing ashless dispersants include oil-soluble salts, amides, imides, oxazolines and esters of long-chain hydrocarpyl-substituted carboxylic acids or anhydride or ester derivatives thereof or mixtures thereof. wherein the long chain hydrocarbyl group is typically selected from the group consisting of 02-C+o (e.g. 02-C5
) is a polymer of monoolefin, and this polymer has about 70
It has a number average molecular weight of 0-5000.

Long-chain hydrocarbyl-substituted dicarboxylic acid materials that may be used to prepare the dispersants include long-chain hydrocarbon polymers (generally polyolefins) and (i) monounsaturated 04-01e dicarboxylic acids [where (a>carboxyl group)]. and (b) at least one, preferably both, of said adjacent carbon atoms become part of said monounsaturation]; or
i> Derivatives of component (i) such as anhydrides or O1-C5 alkyl-derived mono- or di-
Includes reaction products with esters. Upon reaction with the hydrocarbon polymer, the monounsaturation of the dicarboxylic acid material becomes saturated. For example, maleic anhydride becomes hydrocarbyl-substituted anhosohanoic acid.

Typically from about 0.7 to about 4.0 (e.g. 0.8 to 2
．． 6) Charge the reactor with preferably about 1.0 to about 2.01, particularly preferably about 1.1 to about 1.7 moles of said unsaturated C4-C1 dicarboxylic acid material per mole of added polyolefin. do.

Generally, not all polyolefins react with unsaturated acids or derivatives, and hydrocarbyl-substituted dicarboxylic acid materials contain unreacted polyolefins. Unreacted polyolefins are not removed from the reaction mixture in a negative manner (because this type of removal is difficult and industrially impossible) and unreacted monounsaturated 04-C10 The product mixture from which the dicarboxylic acid material has been stripped is further reacted with an amine or alcohol as described above to produce a dispersant.

The average number of moles of dicarboxylic acid, anhydride or ester reacted per mole of polyolefin (reacted or not) added to the reaction is characterized herein as functionality. This functionality (11i) is based on (i) measurement of the saponification number of the resulting product mixture using potassium hydroxide and (ii) measurement of the number average molecular weight of the added polymer by techniques well known in the art. The functionality is
It is defined only with respect to the product mixture obtained. Therefore, the silver of the reacted polyolefin contained in the resulting product mixture can be subsequently modified, i.e. increased or decreased by techniques known in the art, but this type of modification does not change the functionality as described above. . The term hydrocarbyl-substituted dicarboxylic acid material is intended to mean the product mixture whether or not it has undergone this type of modification.

Thus, the functionality of the hydrocarbyl-substituted dicarboxylic acid material is typically at least about 0.5, preferably at least about 0.8, and particularly preferably at least about 0.9.
and typically from about 0.5 to about 2.8 (e.g. 0.6 to 2), preferably from about 0.8 to about 1.4, particularly preferably from about 0.9 to about 1.3. can vary within the range of

Examples of unsaturated mono- and di-carboxylic acids or their anhydrides and esters of this type are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chlormaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid. acids, cinnamic acid, etc.

Suitable olefin polymers for reacting with unsaturated dicarbons or derivatives thereof are polymers consisting of multimolar amounts of C2-Coo (e.g. 02-C5) monoolefins. Olefins of this type include ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene, and the like.

The polymers can be homopolymers, such as polyisobutylene, as well as copolymers of two or more of these olefins, such as copolymers of:
Ethylene and propylene; butylene and isobutylene: propylene and isobutylene, etc. Other copolymers contain a small molar amount (for example, 1 to 10 mol%) of the copolymer monomer
4-c18 non-conjugated diolefins, such as copolymers of isobutylene and butadiene or copolymers of ethylene, propylene and 1,4-hexadiene.

In some cases, the olefin polymer can also be fully saturated, such as ethylene-propylene copolymers made by Ziegler-Nata synthesis using hydrogen as a regulator to control molecular weight.

The olefin polymer used in the dispersant is generally about 700
~5,000, more typically from about 800 to about 3
,000. Particularly useful olefin polymers have number average molecular weights ranging from about 900 to about 2,500 and have about one terminal double bond per polymer chain. A particularly useful starting material for this is polyisobutylene. The number average molecular weight of such polymers can be determined by several known techniques. A convenient method for determination is gel permeation chromatography (GPC). It also provides information on the molecular weight distribution [W, W, Yau, J, J, Kirkland &amp; Sands Corporation, New York (197
9) ].

Methods of reacting olefin polymers with 04-io unsaturated dicarboxylic acids, anhydrides or esters are known in the art. For example, olefin polymers and dicarboxylic acids or derivatives are simply described in U.S. Pat.
No. 3,401,118, it may be heated to bring about the ene reaction. Alternatively, the olefin polymer can be first halogenated to about 1 to about 8%, preferably 3 to 7% by weight chlorine or bromine, based on the weight of the polymer, such as by passing chlorine or bromine through the polyolefin. 60-250
Approximately 0.5 at a temperature of °C (e.g. 120-160 °C)
Chlorination or bromination can be carried out for up to 10 hours, preferably 1 to 7 hours. The halogenated polymer is then treated with sufficient unsaturated acid or derivative at 100-250°C so that the resulting product contains the desired number of moles of unsaturated acid or derivative per mole of halogenated polymer.
Generally at about 180-235°C for about 0.5-10 hours,
For example, the reaction can be carried out for 3 to 8 hours. A general method of this type is described in U.S. Pat. No. 3,087,936.
No. 3.172.892@, No. 3.272.746, etc.

Alternatively, the olefin polymer and the unsaturated acid or derivative are mixed and chlorine is added to the hot substance while heating.

This type of method is described in U.S. Pat. No. 3,215. ．． No. 707, No. 3,231,587, No. 3.912.764, No. 4
．． No. 110.349 and British Patent No. 1,440,219
Disclosed in each publication.

Due to the use of halogens, about 65 to 95 weight percent of the polyolefin (eg, polyisobutylene) is generally reacted with the dicarboxylic acid or derivative. When the thermal reaction is carried out without the use of halogens or catalysts, generally only about 50 to 7
Only 5% by weight of polyisobutylene reacts. Chlorination serves to increase reactivity.

To form the dispersant additive, at least one hydrocarbyl-substituted dicarboxylic acid material is mixed with at least one amine, alcohol (including polyols, amino alcohols, etc.).

If the acid material is further reacted (eg, neutralized), generally at least 50% to all acid units are reacted.

Amine compounds useful as nucleophilic reactants for neutralizing hydrocarbon-substituted dicarboxylic acid materials include heptamines and (preferably) polyamines, particularly preferably about 2 to 60 in total, preferably 2 in the molecule. ~40 pieces (for example, 3
~20) carbon atoms and about 1 to 12, preferably 3 to
12, particularly preferably 3 to 9 nitrogen atoms. These amines may be hydrocarbyl amines or may contain other groups such as hydroxy, flukoxy, amide, nitrile, imidacillin groups, and the like. 1 to 6, preferably 1 to 3
Hydroxyamines having 2 hydroxy groups are particularly useful. Preferred amines are aliphatic saturated amines having the general formula:
C1-C25 straight chain or branched alkyl group, C1-C
I2 alkoxy C2-C6 alkylene group, C2-C12
selected from the group consisting of hydroxyaminoalkylene groups and C1-CI2 alkylamino C2-C6 alkylene groups, and R''' can also represent a group of the general formula: where R' has the above meaning; , and S and S' can be the same or different numbers from 2 to 6, preferably from 2 to 4, and t' is from O to 1
0. They can be the same or different numbers, preferably from 2 to 71, particularly preferably about 3 to 7, with the proviso that t and t'
and the sum of 15 or less 1 amines. To facilitate the reaction, R1R
', R'', R''', s, s', and t' typically have at least one primary or secondary amino group, preferably at least two primary or secondary amino groups and V are preferably selected to be sufficient to provide the compounds.

This is true if at least one of said R, R', R" or R"' groups is selected as hydrogen or if R"' or H is required, or if the Vl group has a secondary amino group, t in formula V. is at least 1. The most preferred amines of the above formula are represented by formula V and contain at least two primary amine groups and at least one, preferably at least three, secondary amine groups. have

Non-limiting examples of suitable amine compounds include: 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,6-diamithexane; polyethylene amines, e.g. Diethylenetriamine; triethylenetetramine: tetraethylenepentamine; polypropyleneamine, such as 1,2-propylene diamine; di(1,2-propylene)triamine; di<1,3-propylene>triamine: N, N
-dimethyl-1,3-diamino-propane; N□, N-
Di(2-aminoethyl)ethylenediamine: N, N-
Di(2-hydroxyethyl)1,3-propylenediamine: 3-dodecyloxypropylamine; N-dodecyl-1,3-propanediamine; Tris-hydroxymethylaminomethane (THAM) diisopropanolamine; Jetanolamine; Ethanolamine; mono-, di- and tritallowamine; aminomorpholine,
For example, N-(3-aminopropyl)morpholine; as well as mixtures thereof.

Other useful amine compounds include: cycloaliphatic diamines, such as 1,4-di(amitumedel)cyclohexane, and heterocyclic nitrogen compounds, such as imidacilline and the general formula (■>: (■) U In the formula, DI, 02 are the same or different, and each is an integer of 1 to 4, and nl, n2, and n3 are the same or different, and each is 1 to 4.
is an integer of 3]. Non-limiting examples of such amines include 2-pentadecyl imidacillin: N-(2-aminoethyl)piperazine, and the like. Commercially available mixtures of amine compounds can be advantageously used. For example, one method for producing alkylene amines involves reacting an alkylene dihalide (e.g., ethylene dichloride or propylene dichloride) with ammonia, which is a complex mixture of alkylene amines in which nitrogen pairs are linked by alkylene groups. and produces compounds such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine and isomeric piperazine. Low cost poly(ethylene amine) compounds having an average of about 5 to 7 nitrogen atoms per molecule are available, such as "Polyamine H", "
Polyamine 400'', [Dow Polyamine E-100J
It is commercially available under product names such as.

In general, useful amines are polyoxyalkylene polyamines, such as those having the formula: %Formula % [) [where m has a value of about 3 to 70, preferably 10 to 35]: and the formula: R+fulkylene+O-alkylene ← Lower NH2] a (IX
) [wherein n has a numerical value of about 1 to 40, the sum of n is about 3 to about 70, preferably about 6 to about 35, and R is a polycarbonate having up to 10 carbon atoms. and the number of substituents on the R group is indicated by [a], which is a number from 3 to 6. The number of alkylene groups in formula (■) or (IX) is about 2 to 7, preferably about 2 to 4.
It can be a straight chain or a branched chain having 5 carbon atoms.

The polyoxyalkylene polyamine of the above formula (■) or (IX), preferably polyoxyalkylene diamine and polyoxyalkylene triamine, has a molecular weight of about 200 to about 4
,000, preferably in the range of about 400 to about 2.000.

Suitable polyoxyalkylene polyamines include polyoxyethylene and polyoxypropylene diamines, as well as polyoxypropylene triamines, with polyoxyalkylene polyamines ranging from about 200 to 2,0
It has an average molecular weight in the range of 0.00. Polyoxyalkylene polyamines are commercially available and are available for example [Chefamine D-230, D-400, [)-1000, [)
-2000 and T-403J from Jefferson Chemical Company.

The amine contains an oil solution containing 5 to 95 wt% of the hydrocarbyl-substituted dicarboxylic acid material at about 100 to 250
℃, preferably 125 to 175℃.
It readily reacts with the selected hydrocarbon-substituted dicarboxylic acid material, such as alkenylsuccinic anhydride, by heating for 10 hours, such as from 2 to 6 hours, until the desired amount of water is removed. Heating is carried out to promote the formation of imides or mixtures of imides and amides rather than amides and salts. The reaction ratio of hydrocarbyl-substituted dicarboxylic acid material to the number of equivalents of amine and other nucleophilic reactants described herein can vary considerably depending on the type of reactants and the type of bond formed. Generally 0.1-1.0, preferably about 0.2-0
. For example, about 0.8 moles of pentamine (having 2 primary amino groups and 5 reaction equivalents of nitrogen per molecule).
to a mixture of amides and imides, i.e. 1 derived from the reaction of polyolefins with maleic anhydride.
, up to a functionality of 6 is preferred. That is, preferably about 0.4 equivalents of pentamine per equivalent of reactive nitrogen of the amine [i.e., 1.60/
(0,8×5) equivalents] of succinic anhydride.

Ashless dispersant esters are obtained by reacting the long chain hydrocarbyl-substituted dicarboxylic acid materials with hydroxy compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols.

Polyhydric alcohols are the most preferred hydroxy compounds;
Preferably, it has from 2 to about 10 hydroxy groups, such as ethylene glycol, diethlene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and other alkylene glycols, having from 2 to about 8 alkylene groups. carbon atoms.

Useful polyhydric alcohols include glycerin, glycerin heptanooleate, glycerin monostearate, glycerin monomethyl ether, pentaerythritol,
Includes dipentaerythritol and mixtures thereof.

In general, ester dispersants include allyl alcohol,
Cinnamyl alcohol, propargyl alcohol, 1-
It can also be derived from unsaturated alcohols such as cyclohexan-3-ol and oleyl alcohol.

Furthermore, other types of alcohols from which the esters of the present invention can be formed also include ether alcohols and amino alcohols, such as oxyalkylene-, oxyarylene-, oxyarylene-, oxyarylene-, etc., having one or more oxyalkylene, aminoalun or aminoaryleneoxyarylene groups. -, aminoalkylene- and aminoarylene-substituted alcohols. These include cellosolve, calpitol-tetrahydroxytrimethylene diamine and about 15
Illustrated by ether alcohols having up to 0 oxyalkylene groups, where the alkylene group has from 1 to about 8 carbon atoms.

Ester dispersants are diesters or acid esters of succinic acid, i.e. partially esterified succinic esters,
It is also possible to use partially esterified polyhydric alcohols or phenols, ie free alcohols or esters with phenolic hydroxyl groups. Mixtures of the above esters are also within the scope of this invention.

Ester dispersants are described, for example, in U.S. Pat.
It can be manufactured by several known methods, such as those exemplified in US Pat. No. 022 and No. 3,836,471.

The hydroxyamines reacted with the long chain hydrocarbyl-substituted dicarboxylic acid materials to form the dispersant include 2-amino-1-butanol, 2-amino 2-methyl-1-propatol, p-(β-hydroxyethyl)- Aniline, 2
-amino-1-propatur, 3-amino-1-propatol, 2-amino-2-methyl-1,3-propane-
Diol, 2-amino-2-ethyl-1,3-propanediol, N-(β-hydroxy-propyl)-N'-
(β-7minoethyl)-piperazine, ] ~ lis(hydroxymethyl)-amino-methane [also known as trismethylolaminomethane], 2-amino-1-
Includes butanol, ethanolamine, β-(β-hydroxyethoxy)ethylamine, and the like. These or similar.

Mixtures of amines can also be used. The above discussion of nucleophilic reactants suitable for reacting with hydrocarbyl-substituted dicarboxylic acid materials includes amines, alcohols, and mixed compounds of amines and dicarboxylic acids having reactive functional groups, ie, aminoalcohols.

Preferred types of ashless dispersants are substituted with succinic anhydride groups and include the polyethylene amines (e.g., tetraethylenepentamine, pentaethylene hexazine), polyoxyethylene and polyoxypropylene amines (e.g., polyoxypropylene diamine, trismethylol). aminomethane) or polyisobutylene reacted with the alcohols mentioned above, such as pentaerythritol, or combinations thereof. One particularly suitable dispersant
Types include succinic anhydride substituted and (i) hydroxy compounds (e.g. pentaerythritol), (ii)
Polyoxyalkylene polyamines, including those derived from polyoxypropylene diamine and/or (iii) polyisobutylene reacted with polyalkylene polyamines such as polyethylene diamine and tetraethylene pentamine. Other suitable types The dispersant of (i) a polyalkylene polyamine (e.g., tetraethylenepentamine) and/or (ii) a polyhydric alcohol or polyhydroxy-substituted aliphatic primary amine (e.g., pentaerythritol or trismethylolaminomethane) including those derived from polyisobutenyl anophosuccinic acid reacted with

2. Reaction products of relatively high molecular weight aliphatic or cycloaliphatic halides and amines, preferably polyalkylene polyamines. These can be characterized as amine "dispersants", examples of which are e.g.
．． No. 555 and No. 3,565,804.

3. Reaction products of alkylphenols in which the alkyl group has at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (particularly polyalkylene polyamines). This can be characterized as a "Mannich dispersant".

Examples include materials described in the following US patent publications: U.S. Patent No. 3,725,277 U.S. Patent No. 3,725. ．． No. 180 U.S. Patent No. 3.726.882 U.S. Patent No. 3.980.569.

4. Carboxyl, amine or Mannich dispersants such as urea, thiourea, carbon disulfide, phosphosulfuryl hydrocarbons, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitrites, epoxides, boron compounds, Products obtained by after-treatment with reagents such as phosphorus compounds. Examples of materials of this type are described in the following U.S. patent publications: U.S. Patent No. 2,805,217; US Pat. No. 3.254.025 US Pat. No. 3.394.179 US Pat. No. 3,511,780 US Pat. No. 3.703.536 US Pat. No. 3.704.308 US Pat. , 708.422; U.S. Patent No. 3,850.822; U.S. Patent No. 4,113,639; U.S. Patent No. 4,116,876.

More particularly, nitrogen- and ester-containing dispersants are preferably used, generally as described in U.S. Pat.
．． Publication No. 254.025 (cited here for reference)
rough treatment by boriding as taught in .

This comprises combining the selected nitrogen dispersant with a boron compound selected from the group consisting of boron oxides, boron halides, 1111 acids, and esters of boric acid in an atomic ratio of about 0.1 atomic ratio of boron per mole of said nitrogen dispersant. This is easily accomplished by treatment with d, which provides about 20 atomic ratios of boron for every 1 atomic ratio of nitrogen in the nitrogen dispersant. Beneficially, the boronated dispersant contains about 0.05% of the total weight of the boronated nitrogen dispersant.
It contains up to 2.0% by weight of boron, such as 0.05 to 2.0% by weight, such as 0.05 to 0.1% by weight. IJR* Boric acid polymer [mainly T (HBO2)] in the product
The boron, which is believed to be present as [3]], is believed to bind to the dispersant imide and diimide as an amine salt, (eg, the meta I [salt] of the diimide).

The treatment is particularly advantageous in that - for boat fishing, about 0.05 to 4%, for example 1 to 3%, added as a slurry to said nitrogen dispersant.
% by weight (relative to the weight of the nitrogen dispersant) of said boron compound, preferably fl acid, and with stirring about 13
This is easily accomplished by heating at 5-190°C, for example 140-170°C, for 1-5 hours, followed by nitrogen stripping in said temperature range. Alternatively, the boron treatment can be performed by adding boric acid to the thermal reaction mixture of the dicarboxylic acid material and the amine while removing the water.

5. Combinations of oil-soluble monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers having polar substituents (such as aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates). Copolymer. These can be characterized as "polymeric dispersants", examples of which are disclosed in the following U.S. patent publications: U.S. Pat. No. 3,329,658; Persistent Grant No. 3,666.730 U.S. Patent No. 3.702.300.

All of the above U.S. patent publications are disclosed for the disclosure of ash dispersants.
It is quoted here for reference.

Lubricating oil flow improvers (LOFIs) modify the size, number and growth of wax crystals in a lubricating oil to provide improved low temperature handling as measured by tests such as pour point and mini-rotational viscosity (MRV). It includes any additives that impart properties, pumpability and/or drivability. Most lubricating oil flow improvers are or contain polymers. There are generally two types of these polymers:
Skeleton type or side chain type.

For example, skeletal types such as ethylene-vinyl acetate (EVA) have methylene segments of various lengths randomly distributed within the backbone of the polymer, and these are bound or cocrystallized with wax crystals to form the polymer. Prevents crystal growth due to branched chains and amorphous segments.

Side-chain polymers, which are the type primarily used as LOFIs, have methylene segments as side chains (preferably as linear side chains). These polymers behave similarly to the skeletal type, except that the side chains have been found to be more effective in treating isoparaffins and n-paraffins present in lubricating oils. A typical example of this type of polymer is C8
~C18 dialkyl fumarate/vinyl acetate copolymer,
polyacrylates, polymethacrylates, and esterified styrene-maleic anhydride copolymers.

Foam control agents can be provided by antifoam agents of the polysiloxane type, such as silicone oils and polydimethylsiloxanes.

Anti-wear agents, as their name implies, reduce wear on moving metal parts. Representative examples of conventional antiwear agents that may be used to supplement the phosphorus and sulfur containing reaction product mixtures of this invention are zinc dialkyldithiophosphates and zinc diaryldithiophosphates. However, it is an important advantage of the present invention that supplementary antiwear agents do not necessarily have to be used and may in fact be excluded from the compositions of the present invention.

Seal swellants include mineral oils of the type that cause swelling, including aliphatic alcohols having from 8 to 13 carbon atoms, such as tridecyl alcohol, with preferred seal swellants having from 10 to 60 carbon atoms. and 2 to 4 bonds, such as dihexyl phthalate, as described in U.S. Pat. No. 3,974,081.

Some of these many additives (eg dispersants, oxidation inhibitors) can provide multiple functions. This means is well known and need not be explained in detail here.

Compositions containing these conventional additives are typically incorporated into the base oil in amounts effective to provide normal accessory functions. Typical (wide range) of additives of this type (preferred) Weight % Weight % 1-12 1-4 o, oi-3 0.01-1.5 0.01-5 0.01-1.5 0. 1-10 0.1-5 0.01-2 0.01-1,5 Composition V, 1. Improver Corrosion inhibitor Oxidation inhibitor Dispersant Lubricating oil flow improver Detergent/Rust inhibitor 0.01-6 0.01-3 Antifoaming agent 0.001-o,io,ooi-0.0
1 Anti-wear agent o, ooi~5 0.001~1
．． 5 Seal swelling agent 0.1-8 0.1-4 Gap modifier 0.01-3 0.01-1.5 Lubricant base oil Balance Balance Therefore, in a broad sense, the hydroxyetheramine compound of the present invention When used in oil compositions, typically in small amounts, it is effective in imparting improved friction-modifying properties as compared to the same composition in which the diroxyether amine compound is not present.

Other conventional additives 1'J0 selected to meet the particular requirements of the selected type of lubricating oil composition may also be included as desired.

Accordingly, any effective amount of hydroxyetheramine additive may be incorporated into the lubricating oil composition, typically from about 0.05 to about 5% by weight, based on the weight of the composition, preferably It is contemplated that this amount will be sufficient to provide a given composition with about 0.08 to about 1% by weight, particularly preferably about 0.1 to about 0.5% by weight of the hydroxylamine additive. Similarly, any effective amount of the above organophosphite 1
-Esters may be used in combination with hydroxyetheramine additives, but the effective amount typically ranges from 0.1 to about 1% by weight, preferably from about 0.2% to about 1% by weight, based on the weight of the composition.
It is believed that this amount is sufficient to provide the oil composition with an amount of phosphite ester additive in an amount of about 0.8% by weight, and particularly preferably from about 0.3 to about 0.6% by weight.

If other additives are used, it is not necessary or an additive concentrate comprising a concentrated solution or dispersion of a hydroxyetheramine compound or a phosphite ester-doxyetheramine compound together with the other additives. It is desirable to create a concentrated additive mixture (hereinafter referred to as an additive package), which allows several additives to be added simultaneously to a base oil to create a lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil can also be facilitated by a solvent and by mixing with mild heating, but this is not necessary.

Concentrates (i.e., additive packages) typically contain a combination of a hydroxyetheramine compound or a phosphite ester and a hydroxyetheramine compound of the present invention and the appropriate additive on a predetermined amount basis. When combined with a lubricant, it is formulated to be present in an amount appropriate to provide the desired concentration in the final composition. For example, a hydroxyetheramine compound or a combination of a phosphite ester and a hydroxyetheramine compound can be added to a small amount of a base oil or a compatible solvent along with other desired additives to is about 0.1 to about 50% by weight as active ingredient, preferably about 0.7 to about 25% by weight, particularly preferably about 1.0% by weight.
A concentrate containing the appropriate proportions of ~10% by weight of additives is formed.

The final composition was formulated using approximately 10% by weight of the additive package. The remainder is base oil.

All weight percentages listed above are the active ingredients of the additive (a, i,)
content and/or additive package (i.e. each additive's a, i, weight plus total or diluent weight, h)
Based on the weight of the composition (1).

As mentioned above, the organic bosphite esters contemplated for use in the present invention are characterized as having good compatibility with hydroxyetheramine compounds. Therefore, lubricating oil compositions containing both of these additives exhibit excellent friction stability. This has the added advantage of reducing the amount of hydroxyetheramine compound or other friction modifier required to achieve the overall desired friction modification. Is the amount of hydroxy ether amine compound or other friction modifier A
It was found that the more it increases during TF, the lower the breakaway static pressure torque becomes. The lower the breakaway static torque (and the breakaway static friction coefficient), the more susceptible automatic transmission bands and clutches are to slip. therefore,
Adjust the amount of friction modifier (and thus any relevant friction stability promoter) without sacrificing the fluid's friction modifying properties (as measured by the torque difference To-TD, for example) and its stability. , for example, it is highly advantageous to reduce the air flow. This is because this facilitates achieving both the desired breakaway static pressure torque and torque differential friction characteristics simultaneously.

In summary, the combination of an organophosphite ester and a hydroxyether amine compound provides flexibility for manufacturers to process ATF to achieve the balance of properties required by today's relatively stringent transmission manufacturer specifications. enable.

[Example] The present invention will be further explained below with reference to Examples.

However, it should be understood that the invention is not limited only to these examples. In the examples and other descriptions herein, all parts and percentages are based on tit unless otherwise specified.

Example 1 Formula: [wherein X is O, R1 is a C18 aliphatic hydrocarbon group, R3 is H, R2 is a C3 alkylene, and R4 and R5 are both C2 alkylene groups] , p, and p' are each 1] First, a hydroxyetheramine compound of 27
0 parts by weight of octadecenyl alcohol is mixed with 53 parts by weight of acrylonitrile in the presence of an acidic or basic catalyst.
It was made by reacting at temperatures ranging from 0 to 60°C for about 6 hours to produce the ethernitrile intermediate. The intermediate is then catalyzed from 140 to 140 in the presence of a Raney nickel catalyst.
The ether amine was produced by hydrogenation at a temperature in the range of 150°C for about 2 hours. This ether amine was then reacted with 44 parts by weight of ethylene oxide in the presence of a basic catalyst at a base temperature in the range of about 150° C. for 6 hours to yield the hydroxy ether amine product.

Example 2 An ATF base fluid, hereinafter referred to as test base, was formulated with intermediate doses of seal swell additive, dispersant, antioxidant, viscosity index improver, and mineral oil base.

To the test base sample was added 0.5% by weight of triphenyl phosphite (TPP) and 0.2% by weight of thiobisethylenedodecyl succinic acid half ester having the formula: The resulting composition is referred to as Comparative Composition 1C.

Other samples in the test base included 0.2ffiffi% C4
/C5 dialkyldithiophosphate (ZDDP) and 0
．． 2% by weight of a hydroxyetheramine friction modifier made according to Example 1 was added. The resulting composition is referred to as Comparative Composition 2C.

Other samples in the test base included 0.2 wt% ZDDP and 0
．． 2% by weight of the same friction modifier used in Composition 1C was added. The resulting composition is referred to as Comparative Composition 3C.

Other test base samples include 0.5% TPP and 0.2% by weight TPP.
% by weight of the same hydroxyetheramine friction modifier used in Composition 2C. The resulting composition is referred to as Composition 4.

To another test base sample, 0.5% by weight of dioleyl phosphite (DOP>) and 0.2% by weight of the same hydroxyetheramine friction modifier used in Composition 4 were added. The composition obtained was referred to as Comparative Composition 5G.

The compositions of Compositions 10-5C are summarized in Table 1 below: Ingredients, wt% Dioleyl Phosphite 1- Triphenyl Phosphite Hydroxy Ether Amine Succinic Acid Half Ester (Formula IV) Zinc Dialkyl Dithiophosphate Test Base Table 1 Composition N0 10203C4 C O25 0,5--- 0,5 0,2 0,2 0,2 0,2 0,2 0,2 0,2--- 99,399,699,699,399 , 3 The above compositions were then tested according to the modified 5AENα friction test and the Vicars AW test.

4000 Nykle Friction Test This test uses a SAE No. 2 Friction Machine, which is suitably operated for 4000 cycles, in which abnormal latch plate wear or composition - face spray 1
No wear and tear occurs. The test was conducted as a continuous series of 20 second cycles, each cycle consisting of three phases: Phase I (10 seconds) - Motor speed 3, 60 rpm, clutch plate engaged; Phase II (5 seconds) - Motor reduced. phase l11 (5 seconds) motor de-energize and clutch plate released. 2.812kg/cm2 (40ps+)
4000 cycles were repeated using a flywheel energy of 20.740 Joules with an applied clutch pressure of . While engaging the clutch, the friction torque is recorded as a function of time as the motor speed decreases from 360 Orpm to 0. The torque trace shows that the intermediate point between the start and end of clutch engagement (i.e. motor speed 1)
800 ppm) and determine the dynamic torque (TD) at
The torque (To) is measured between. motor speed is 3
The time (seconds) required for the phase (2) to decrease from 60 Orpm to 0 is called the stop time. Next, the torque ratio of the oil composition is determined from (To/TO>). In addition to determining the dynamic torque (T t ) at the midpoint and the static torque (To), the breakaway static torque (breakaway 5tat) is determined.
ictor-que) (T3) is also determined. This makes the composition plate 2.812kMcm2
(40 psi) while fixing the steel reaction plate to prevent it from rotating. Torque is then measured until slip occurs. Record the maximum 1-lux observed as Ts. The withdrawal static pressure torque ratio (TsZTD) is determined from Ts.

The breakaway static torque ratio accounts for the transmission's ability to resist slip. The lower this ratio, the greater the slip.

The test results for Compositions 10-5C are shown in Table 2.

The data shown in Table 2 is for 200 cycles and 4000 cycles.
Measurements were taken after operation of the cycle.

As can be seen from Table 2, Composition 1C resulted in unacceptable ToZTD values at 200 cycles. 200
Ts of 19 for composition 1C and 24 for composition 3C measured between cycles and 4ooo cycles
The change is much greater than that obtained with composition 4. Composition 2C exhibits acceptable friction data, but as seen below with respect to vicarous wear data, composition 2C
shows poor wear properties. Therefore, composition 1C12
It will be clear that C and 3C represent a less desirable composition.

Composition 4 has TD, Ts, T () after 200 cycles.
/ T () all showed acceptable values.

T□/T□ of 0.99 after 200 cycles
The value is at the upper end of the acceptable range and provides a satisfactory shift feel for the vehicle. A comparison of the 200 cycle data and the 4000 cycle data shows the friction durability. This comparison shows that for composition 4, Ts
It can be seen that the value does not change by only 5N, mu. This change is much lower than the permissible change for testing. This data shows that Composition 4 exhibits excellent friction retention and meets all acceptable parameter ranges listed above.

For composition 5C, the data are below the acceptable range of 400
Ts at 0 cycle and To at 200 and 4000 cycles
ZTD value is shown.

Thus, the data in Table 2 shows that the friction properties of ATFs formulated with the hydroxyamine friction modifiers of the present invention are different from those of similar ATFs containing conventional friction modifiers that are outside the scope of the present invention.
It shows that it is superior to the composition.

Vicars Abrasion Test This vane pump abrasion test is fully described in ASTM method [2882]. It demonstrates the wear characteristics of petroleum and non-petroleum hydraulic fluids using constant volume high pressure vane pumps.

The method used for the tests conducted here was based on the pump outlet pressure [
γ1.3k(]/Cm2 (10001)Si) vs. 142.6kq/cm2 (2000psi)]
and A only at a liquid temperature of 79.4°C (175°F)
It is different from STM 02882.

The conditions for this test are as follows: Pump outlet pressure 70.3±1.41 kg/
cm2 (1000±20pSi) Liquid temperature, pump inlet Approx. 79.4°C (175±5
D) Pump speed 1200±60rpm Liquid filling 11.3612 (3 gallons)
A Vikas 104C vane pump car 1-ridge was used for this test. After the 24 hour test period has ended and again after the 100 hour test period has ended, the cam ring and vanes are measured for total weight loss. The maximum weight loss allowed in this test is 15 mg.

The test results for compositions 1C to 5C are shown in Table 3.

Table 3 Vicars abrasion resistance test Composition Vicars ring and vane weight regression (m()) 1Ω 2C4 ±-, 1924 hours 3.8 329.1 25.0 0.8 2.
8100 hours 10.1 634.2 73.4 5
．． 6 3.9 As can be seen with reference to Table 3, the results for Composition 4 containing both a hydroxyetheramine friction modifier and triphenyl phosphite are similar to those of the same hydroxyetheramine friction modifier. but containing either ZDDP (composition 2C) or dioleyl phosphite (composition 5C) instead of triphenyl phosphite, including compositions 2C and 5C. is also excellent. Only Composition 5C at 100 hours had good abrasion properties, but as shown in Table 2, this composition showed poor abrasion performance when amber was substituted for the hydroxyetheramine friction modifier. Compositions using acid half ester friction modifiers can be used such as this composition, triphenylphosphite (Composition 1C) or ZDDP (Composition 1C).
Whether or not it contains any of composition 3C),
The test results were poor.

Collectively, the data in Tables 2 and 3 demonstrate that triphenylphosphite (TPP), when used in combination with hydroxyether amines, can be used as an antiwear additive for ZDD.
This shows that it is more advantageous than P or dioleyl phosphite.

Although the principles, preferred embodiments, and modes of operation of the present invention have been explained above, the present invention is not limited to these specific examples, and it is natural that various modifications may be made without departing from the spirit and scope of the present invention. I hope the businesses will understand.

Claims (29)

[Claims] (1) In a lubricating oil composition suitable for use as an automatic transmission fluid, the formula for (a) mineral oil and (b) friction modification amount: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, indicates O or S, and R_1 is C_3 to C
_2_7 represents a saturated or unsaturated aliphatic hydrocarbon group,
R_2 represents a linear or branched C_1 to C_6 alkylene group, R_3 represents H or CH_3, and R_4 and R_5 independently represent a linear or branched C_
2-C_5 alkylene group] and having a total of 10 to 30 carbon atoms, boronated or non-boronated hydroxyetheramine compound. (2) The lubricating oil composition according to claim 1, wherein X is O and R_2, R_4 and R_5 are linear alkylene groups. (3) The lubricating oil composition according to claim 2, wherein R_1 represents a C_1_6 to C_2_0 alkylene group and R_2 represents a C_2 to C_4 alkylene group. (4) R_1 is C_1_8 alkylene, R_2 is C_3 alkylene, R_3 is H, and R_
4. The lubricating oil composition of claim 3, wherein 4 and R_5 are C_2 alkylene. (5) The lubricating oil composition according to claim 3, wherein the hydroxyetheramine compound is boronated. (6) an amount effective to impart wear resistance to the composition; the formula: ▲ May be a mathematical formula, a chemical formula, a table, etc. ▼ [wherein R_6 is selected from the group consisting of aryl and C_1 to C_3 alkaryl; represents a hydrocarbyl group, and R_7 and R_8 are independently C_1 to C_2_5.
Alkyl, aryl, C_1-C_3 alkaryl, C
The lubricating oil composition according to claim 1, further comprising an organic phosphite ester having a hydrocarbyl group selected from the group consisting of _5 to C_8 cycloalkyl and halo-substituted derivatives thereof. (7) The lubricating oil composition according to claim 6, wherein R_1 represents a C_1_6 to C_2_0 alkylene group, and R_2 represents a C_2 to C_4 alkylene group. (8) R_1 is C_1_8 alkylene, R_2 is C_3 alkylene, R_3 is H, and R_
8. The lubricating oil composition of claim 7, wherein 4 and R_5 are C_2 alkylene. (9) The lubricating oil composition according to claim 8, wherein X=O. (10) The lubricating oil composition according to claim 9, wherein the hydroxyetheramine compound is boronated. (11) Organic phosphite is 0.1 based on the weight of the composition
11. The lubricating oil composition of claim 10, wherein the lubricating oil composition is present in an amount of -1% by weight. (12) The lubricating oil composition according to claim 11, wherein R_6, R_7 and R_8 are selected from the group consisting of alkyl, aryl and alkaryl groups. (13) The lubricating oil composition according to claim 12, wherein R_6, R_7 and R_8 are selected from the group consisting of aryl groups. (14) The lubricating oil of claim 9, further comprising an effective amount of at least one additional compound to impart at least one of antioxidant properties, seal swelling properties, dispersibility properties, and viscosity modification properties to the composition. Composition. (15) The lubricating oil of claim 5, further comprising at least one additional compound in an amount effective to impart at least one of antioxidant properties, seal swelling properties, dispersibility, and viscosity modifying properties to the composition. Composition. (16) The lubricating oil of claim 3, further comprising at least one additional compound in an amount effective to impart at least one of antioxidant properties, seal swelling properties, dispersibility, and viscosity modifying properties to the composition. Composition. (17) The lubricating oil of claim 4, further comprising at least one additional compound in an amount effective to impart at least one of antioxidant properties, seal swelling properties, dispersibility, and viscosity modifying properties to the composition. Composition. (18) Claim 13 further comprising at least one additional compound in an amount effective to impart at least one of antioxidant properties, seal swelling properties, dispersibility properties, and viscosity modification properties to the composition.
The described lubricating oil composition. (19) The lubricating oil of claim 1, further comprising at least one additional compound in an amount effective to impart at least one of antioxidant properties, seal swelling properties, dispersibility, and viscosity modifying properties to the composition. Composition. 20. The lubricating oil composition of claim 1, further comprising triphenyl phosphite in an amount sufficient to impart wear resistance to the composition. (21) The lubricating oil composition of claim 4 further comprising triphenyl phosphite in an amount sufficient to impart wear resistance to the composition. (22) The lubricating oil composition according to claim 1, wherein X is S. (23) The lubricating oil composition according to claim 22, wherein R_1 represents a C_1_6 to C_2_0 alkylene group, and R_2, R_4, and R_5 are linear alkylene groups. (24) R_1 is C_1_8 alkylene, R_2
is C_3 alkylene, R_3 is H, and R_
24. The lubricating oil composition of claim 23, wherein 4 and R_5 are C_2 alkylene. (25) further comprising at least one additional compound in an amount effective to impart at least one of antioxidant properties, seal swelling properties, dispersibility properties, and viscosity modification properties to the composition.
The described lubricating oil composition. (26) The lubricating oil composition according to claim 8, wherein X is S. (27) The lubricating oil composition according to claim 26, wherein R_6, R_7 and R_8 are selected from the group consisting of alkyl, aryl and alkaryl groups. (28) The lubricating oil composition according to claim 27, wherein R_6, R_7 and R_8 are selected from the group consisting of aryl groups. (29) further comprising at least one additional compound in an amount effective to impart at least one of antioxidant properties, seal swelling properties, dispersibility properties, and viscosity modification properties to the composition.
The described lubricating oil composition.