JP2796358B2 - Lubricating oil composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Cross-Reference of Related Applications This application is a continuation-in-part of the pending application Serial No. 206,113, filed June 13, 1988. The disclosure of the earlier application is fully set forth herein. A priority under 35 USC 120 is claimed for the disclosure contained in the earlier application Serial No. 206,113.

(Industrial application field) This invention relates to a lubricating oil composition. In particular, the invention relates to lubricating oil compositions containing oils of lubricating viscosity, carboxylic acid derivative compositions exhibiting both VI and dispersing properties, and at least one metal salt of dithiophosphoric acid.

BACKGROUND OF THE INVENTION Lubricants used in internal combustion engines (particularly spark ignition engines and diesel engines) are constantly being modified and improved to obtain improved performance. Various mechanisms, including SAE (Society of Automotive Engineers, Society of Auto
motive Engineers), ASTM (formally the American Society for Testing
and Materials) and API (American Petroleum Institute, American
Not only the Petroleum Institute), but also the auto industry is constantly demanding to improve the performance of lubricating oils. Through the efforts of these organizations, various standards have been established and refined over the years. The engine has increased power and complexity,
Performance requirements for obtaining the following lubricating oils are increasing. The lubricating oil has a low tendency to degrade under conditions of use, thereby reducing wear and reducing the formation of undesirable precipitates such as: The precipitate includes, for example, varnish, sludge, carbon-containing substances and resinous substances. These tend to stick to various engine parts and reduce the efficiency of the engine.

In general, for crankcase lubricants that can be used in spark-ignition engines and diesel engines, different classifications and performance requirements for oils due to differences in lubricants in these applications and the requirements that exist in these lubricants. Established High quality commercial oils designed for spark ignition engines have recently been identified and designated as "SF" oils when they can meet the performance requirements of API Service Class SF. In recent years, a new API service class SG has been established and this oil may be labeled "SG". Oils denoted as SG, API Service Class S
G performance requirements must be met. The SG performance requirements have been established to ensure that these new oils have more desirable properties and performance potentials than those required for SF oils. The SG oil can be designed to minimize engine wear and deposits and to minimize thickening during use. This SG oil is intended to improve engine performance and durability compared to all conventional engine oils sold for spark ignition engines. An additional feature of SG Oil is that the SG specification has included requirements for CC category (diesel).

In order to meet the performance requirements of SG oil, it must successfully pass the following gasoline and diesel engine tests established as industry standards: Ford Sequence VE test; Buick Sequence III E Test; Oldsmobile Sequence I
ID test; CRC L-38 test; and Caterpillar single cylinder test engine 1H2. This caterpillar test is low (1
Performance requirements are also included to adapt the oil to diesel applications for inht duty (diesel performance classification "CC"). In addition, SG-classified oil is used for heavy duty diesel applications (diesel class “C
D "), this oil formulation must pass the more stringent performance requirements of the Caterpillar Single Cylinder Test Engine 1G2. All the requirements of these tests have been , And this test is described in more detail below.

When it is desirable for an SG-class lubricant to also exhibit improved fuel economy, it must meet the requirements of the Sequence IV fuel efficiency engine oil dynamometer test.

A new classification of diesel engine oil is also available at SA
Established with the combined achievements of E, ASTM and API. New diesel oil will be labeled "CE". Oils that meet the new diesel classification CE
CD category (including Mack T-6 exam, Mack T-7
Test, and Cummins NTC-400 test), which need to be able to meet additional performance requirements not found.

An ideal lubricant for most applications should have the same viscosity at all temperatures. However, available lubricants deviate from this ideal. To minimize the viscosity change with temperature, the substance added to the lubricant may be a viscosity modifier, a viscosity improver, a viscosity index improver, or
It is called a VI improver. Generally, substances that improve the VI properties of lubricating oils are oil-soluble organic polymers. These polymers include polyisobutylene, polymethacrylate (ie, copolymers of alkyl methacrylates of various chain lengths); copolymers of ethylene and propylene; hydrogenated block copolymers of styrene and isoprene;
And polyacrylates (ie, copolymers of alkyl acrylates of various chain lengths).

Other materials are included in the lubricating oil composition so that the composition meets various performance requirements. These include dispersants, detergents, friction modifiers, corrosion inhibitors and the like. Dispersants are used in lubricants to keep impurities (especially those formed during operation of the internal combustion engine) in suspension rather than to precipitate them as sludge. Materials exhibiting both viscosity improving and dispersing properties have been described in the prior art. One type of compound having both properties consists of a polymer backbone, to which one or more monomers having polar groups are attached. Such compounds are often prepared by a grafting operation. Here, the skeletal polymer is directly subjected to a reaction with a suitable monomer.

Dispersion additives for lubricants containing the reaction product of a hydroxy compound or amine with a substituted succinic acid or derivative thereof have also been described in the prior art.
Typical dispersants of this type are described, for example, in U.S. Pat.
Nos. 2,746; 3,522,179; 3,219,666; and 4,234,435. When mixed with a lubricating oil, the compositions described in the '435 patent function primarily as dispersants / cleaners and viscosity index improvers.

SUMMARY OF THE INVENTION A lubricating oil formulation useful in internal combustion engines is described. More specifically, a lubricating oil composition for an internal combustion engine comprises (A)
Mixture of a major amount of oil of lubricating viscosity, (B) at least 2.0% by weight of at least one carboxylic acid derivative composition produced by the following reaction, and (C) a metal salt of dihydrocarbyl phosphorodithioic acid About 0.05% by weight
The reaction of (B) above comprises (B-1) at least one substituted succinic acylating agent and (B-2) at least one in the structure. Reaction with at least one amine compound characterized by the presence of a HN <group. Here, the substituted succinic acylating agent comprises a substituent and a succinic acid group. Here, the substituent is derived from a polyalkene. The polyalkene has an n value from about 1300 to about 5000, and about 1.5.
It is characterized by a w / n value of about 4.5. The acylating agent is on average at least for each equivalent of substituent.
1.3 succinic groups are characterized by their presence in the structure. Here, in at least one of the dihydrocarbyl phosphorodithioic acids, one of the hydrocarbyl groups (C-1) is an isopropyl group and a secondary butyl group, and the other hydrocarbyl group (C-2) Contains at least 5 carbon atoms. At least about 20 mole percent of all of the hydrocarbyl groups present in (C) are isopropyl groups, secondary butyl groups, or mixtures thereof. However, when the lubricating oil composition is about (B)
When containing no more than 2.5% by weight, at least about 25 mole percent of the hydrocarbyl groups in (C)
An isopropyl group, a secondary butyl group, or a mixture thereof. In some embodiments, the oil composition contains at least about 0.05% by weight of isopropyl groups, secondary butyl groups, or mixtures thereof, which are derived from a mixture of metal salts of phosphorodithioic acid (C). I do.
The oil composition may also include other desirable additives, such as (D) at least one neutral or basic alkaline earth metal salt of at least one acidic organic compound, and / or (E) at least one Carboxylic acid ester derivatives). In one embodiment, the oil composition of the present invention comprises the above additive and the above additive in an amount sufficient to allow the oil to meet the full performance requirements of the API service class, denoted as "SG". Contains other additives described herein. And, in another embodiment, the oil composition of the present invention comprises the above additives and other additives in amounts sufficient to satisfy the requirements of the API service class, denoted as "CE". Containing additives.

DETAILED DESCRIPTION OF THE INVENTION Throughout this specification and claims, references to weight percent of various components, except for component (A), which is an oil, are on a chemical basis unless otherwise indicated. . For example, if the oil composition of the invention comprises at least 2
When described as containing by weight (B), the oil composition has, on a chemical basis, at least 2% by weight.
(B). Therefore, component (B) is 50% by weight.
If available, a solution of at least 4% by weight of the oil would be included in the oil composition.

The number of equivalents of the acylating agent depends on the total number of carboxylic acid functions present. In determining the number of equivalents of the acylating agent, those carboxyl functions that cannot react as carboxylic acylating agents are excluded. However,
Generally, in these acylating agents, there is one equivalent of acylating agent for each carboxy group. For example, it is present in two equivalents in the anhydride derived from the reaction of one mole of olefin polymer with one mole of maleic anhydride. Conventional methods rely on the number of carboxyl functions (eg, acid number,
It is readily available to determine the valency.
Therefore, the number of equivalents of the acylating agent can be easily determined by those skilled in the art.

The equivalent of an amine or polyamine is the molecular weight of the amine or polyamine divided by the total number of nitrogens present in the molecule. Therefore, ethylenediamine is
Diethylenetriamine has an equivalent weight equal to 1/3 of its molecular weight; diethylenetriamine has an equivalent weight equal to 1/3 of its molecular weight;
The equivalent weight of a commercially available mixture of polyalkylene polyamines is determined by the atomic weight of nitrogen (14) by the% N contained in the polyamine.
And multiply by 100; therefore, a polyamine mixture containing 34% N
It has an equivalent weight of 41.2. The equivalent of ammonia or monoamine will be its molecular weight.

The equivalent weight of a hydroxy-substituted amine that is subjected to a reaction with an acylating agent to form a carboxylic acid derivative (B) is a value obtained by dividing its molecular weight by the total number of nitrogen groups present in the molecule. For the purposes of this invention in preparing component (B), hydroxyl groups are ignored when calculating the equivalent number. Therefore, ethanolamine has an equivalent weight equal to its molecular weight, and diethanolamine has an equivalent weight (nitrogen base) equal to its molecular weight.

The equivalent weight of the hydroxy-substituted amine used to form the carboxylic ester derivative (E) useful in this invention is the molecular weight divided by the number of hydroxy groups present. Any nitrogen atoms present are ignored. Thus, for example, when preparing an ester from diethanolamine, its equivalent weight is 1 / the molecular weight of diethanolamine.
2

The terms "substituent" and "acylating agent" and "substituted succinic acylating agents" are to be given their ordinary meaning. For example, a substituent may be
An atom or group of atoms replaced by another atom or group in the molecule. The term acylating agent or substituted succinic acylating agent refers to the compound itself and does not include the unreacted reactants used to form the acylating agent or substituted succinic acylating agent.

(A) Oil with lubricating viscosity The oil used in preparing the lubricant of the present invention can be based on natural oils, synthetic oils, or mixtures thereof.

Natural oils include animal and vegetable oils (eg, castor oil, lard oil) as well as mineral lubricating oils (eg,
Liquid petroleum oils and mineral lubricating oils of paraffinic, naphthenic or mixed paraffin-naphthenic type and solvent-treated or acid-treated). Oils of lubricating viscosity derived from coal or shale are also useful.
Synthetic lubricating oils include the following hydrocarbon oils and halo-substituted hydrocarbon oils. The hydrocarbon oils and halo-substituted hydrocarbon oils include, for example, polymerized olefins and mixed-polymerized olefins (eg, polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, etc.); -Hexene), poly (1-octene), poly (1-decene), and the like, and mixtures thereof; alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) -benzene, and the like); Polyphenyl (eg, biphenyl, terphenyl, alkylated polyphenyl, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologs thereof, and the like.

Alkylene oxide polymers and mixed polymers and derivatives thereof (in this derivative, the terminal hydroxyl groups have been modified by esterification, etherification, etc.)
It constitutes another class of known synthetic lubricating oils which can be used. These are oils prepared by the polymerization of ethylene oxide or propylene oxide, alkyl ethers and aryl ethers of these polyoxyalkylene polymers (eg, methyl polyisopropylene glycol ether having an average molecular weight of about 1000, molecular weight of about 500-1000). Diphenyl ethers of polyethylene glycol having a molecular weight of about 1000-1500, or diethyl ether of polypropylene glycol having a molecular weight of about 1000-1500, or their mono- and polycarboxylic esters (eg, acetates of tetraethylene glycol, mixed C ₃ -C _8). It is exemplified by fatty acid esters, or the C ₁₃ oxo acid diester).

Other suitable classes of synthetic lubricants that can be used include:
Dicarboxylic acids (eg, phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalon And esters of various alcohols (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, Dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, 1 mol of sebacic acid and tetraethylene glycol 2
And a complex ester formed by reaction with 2 mol of 2-ethylhexanoic acid and the like.

Esters useful as synthetic oils also, C ₅ -C ₁₂ monocarboxylic acids and polyols and polyol ethers (e.g., neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol,
Tripentaerythritol).

Silicon-based oils, such as polyalkyl-, polyaryl, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils, constitute another useful class of synthetic lubricants. This includes, for example, tetraethyl silicate, tetraisopropyl silicate, tetra (2-ethylhexyl) silicate, tetra (4-methylhexyl) silicate, tetra (p
-Tert-butylphenyl) silicate, hexyl- (4
-Methyl-2-pentoxy) disilicate, poly (methyl) siloxane, poly (methylphenyl) siloxane and the like. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresol phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.),
Polymerized tetrahydrofuran and the like are included.

Unrefined, refined and rerefined oils, which are either natural or synthetic oils of the type disclosed above, even if a mixture of any two or more of these Good) can be used in the lubricants of the present invention.
Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example,
Shale oil obtained directly from the retorting operation, petroleum oil obtained directly from the first stage distillation, or ester oil obtained directly from the esterification step and used without further treatment is an unrefined oil. Refined oils are similar to the unrefined oils except they have been further processed in one or more purification stages to improve one or more properties. Many such purification methods are known to those skilled in the art. The methods include, for example, solvent leaching, hydrotreating, secondary distillation, acid or base extraction, filtration, osmosis, and the like. Rerefined oils are obtained by processes similar to those used to obtain refined oils. This process applies to refined oils already used at the facility. Such rerefined oils are also known as reclaimed or reprocessed oils, and are often additionally added to waste additives and methods directed to remove oil breakdown products. It is processed.

(B) Carboxylic acid derivative Component (B) useful in the lubricating oil of the present invention is at least one carboxylic acid derivative composition produced by the following reaction: ) At least one
Reaction of one or more substituted succinic acylating agents with (B-2) at least one amine compound containing at least one HN <group. Here, the acylating agent comprises a substituent and a succinic acid group. Wherein the substituent is derived from a polyalkene characterized by: The polyalkene has an n value from about 1300 to about 5000, and about 1.
It is characterized by a w / n ratio of 5 to about 4.5. The acylating agent is characterized by an average of at least about 1.3 succinic groups in its structure for each equivalent of substituent. Generally, the reaction involves from about 0.5 equivalents to about 2 moles of the amine compound per equivalent of acylating agent.

The carboxylic acid derivative (B) is included in the oil composition in order to improve the dispersibility and VI characteristics of the oil composition. Generally, from about 2.0% to about 10% or 15% by weight of component (B) can be included in the oil composition. However, the oil composition preferably contains at least 2.5% by weight, often at least 3% by weight, of component (B).

Used when preparing the carboxylic acid derivative (B),
The substituted succinic acylating agent (B-1) has 2
It can be characterized by the presence of two groups or moieties. The first group or moiety is conveniently referred to hereafter as a "substituent" and is derived from a polyalkene. The polyalkene from which this substituent is derived has an n value (number average molecular weight) of about 1300 to about 5000, and a w value of at least about 1.5.
/ n value, more usually about 1.5 to about 4.5 or about 1.5 to
It is characterized by a w / n value of about 4.0. Abbreviation w
Is a conventional symbol representing the weight average molecular weight. Gel permeation chromatography (GPC) is not only a method of obtaining both the weight average molecular weight and the number average molecular weight of a polymer, but also a method of obtaining a total molecular weight distribution of the polymer. For this invention, a class of separated polymers of isobutene and polyisobutene are used as GPC assay standards.

Methods for determining the n and w values of polymers are known and have been described in numerous documents and articles. For example, a method for determining the n and molecular weight distribution of polymers is described in WWYan, JJ Kirkland and DDBly, “Latest Size Exclusive Liquid Chromatography” (J. Wiley & Son
s, Inc., 1979).

The second group or moiety in the acylating agent is referred to herein as the "succinic group". This succinic group is a group characterized by the following structure: Here, X and X 'are the same or different. However, at least one of X and X 'is such that the substituted succinic acylating agent can function as a carboxylic acylating agent. That is, at least one of X and X 'must be such that the substituted acylating agent can form an amide or amine salt with the amino compound. Otherwise, the acylating agent functions as a conventional carboxylic acylating agent. Transesterification and transamidation are considered for the present invention as conventional acylation reactions.

Therefore, X and / or X 'are usually -O
H, -O-hydrocarbyl, -OM ⁺ . Where M
⁺ Is one equivalent of a metal, ammonium cation or amine cation, -NH _2, -Cl, represents -Br, and X and X 'are both in order to form an anhydride, it may be a -O-. The particular identification of an X or X 'group that is not one of the above groups is not critical, as long as its presence does not prevent the remaining groups from participating in the acylation reaction.
However, preferably, X and X 'are each such that both carboxyl functionalities of the succinic acid group (i.e., both -C (O) X and -C (O) X') can participate in the acylation reaction. To be.

One of the imperfect valences in the configuration of Formula I Forms a carbon-carbon bond with a carbon atom at this substituent. Other such imperfect valences, with the same or different substituents, may be completed with similar bonds, but all but one of the valencies are
Usually filled with hydrogen (ie, -H).

Substituted succinic acylating agents are characterized by the presence in their structure of at least 1.3 succinic groups (ie, groups corresponding to Formula I) on average for each equivalent of substituent. Can be For the purposes of this invention, the equivalent number of substituents is considered to be the number obtained by dividing the n value of the polyalkene from which the substituent is derived by the total weight of the substituent present in the substituted succinic acylating agent. Can be Therefore, if the substituted succinic acylating agent is characterized by a total weight of the substituent of 40,000, and if the n-value of the polyalkene from which the substituent is derived is 2000, then the substituted succinic acylating agent is , And a total of 20 (40,000 / 2000 = 20) equivalents of substituents. Thus, a particular succinic acylating agent may also have at least 26 succinic groups in its structure to meet one of the requirements of the succinic acylating agent used in this invention. Must be characterized.

Another requirement of the substituted succinic acylating agents is that the substituent must be derived from a polyalkene characterized by a w / n value of at least about 1.5. The upper limit for w / n is generally about 4.5.
Values of 1.5 to about 4.0 are particularly useful.

Polyalkenes having the above mentioned n and w values are known in the art and can be prepared according to conventional methods. For example, some of these polyalkenes are described and exemplified in US Pat. No. 4,234,435.
The disclosure of this patent for such polyalkenes is set forth herein. Some of such polyalkenes, especially polybutenes, are commercially available.

In a more preferred embodiment, the succinic groups typically correspond to the formula: Here, R and R ′ are each independently —OH,
R and R 'when selected from the group consisting of -Cl, -O-lower alkyl and used together are -O-. In the latter case, the succinic groups are succinic anhydride groups. In a particular succinic acylating agent, not all succinic groups need be the same, but they can be. Preferably, this succinic acid group corresponds to the following formula and also corresponds to a mixture of a compound (III (A)) and a compound (III (B)): A substituted succinic acylating agent wherein the succinic group is
(Identical or different) is within the ordinary skill in the art and can be achieved by conventional methods. This method includes, for example, treating the substituted succinic acylating agent itself (eg, hydrolyzing the anhydride to the free acid), or converting the free acid to the acid chloride with thionyl chloride. Conversion and / or the selection of a suitable maleic or fumaric acid reactant.

As mentioned earlier, the minimum number of succinic groups for each equivalent of substituent is 1.3. The maximum number is generally 4.5
Not exceed. Generally, this minimum number will be about 1.4 succinic groups for each equivalent of substituent. The range based on this minimum number is at least 1.4 to
About 3.5, and more specifically about 1.4 to about 2.5.

In addition to the more preferred substituted succinic groups, where the suitability depends on the number and identity of the succinic groups, for each equivalent of substituent, a further preference is that the substituent is derived It is based on the identity and properties of the polyalkene.

For example, for a value of n, a minimum of about 1300 and about
A maximum value of 5000 preferably ranges from about 1500 to about 5000 is also more preferred. More preferred n values are from about 1500 to about
It is in the range of 2800. The most preferred range of n values is from about 1500 to about 2400.

Before proceeding further with the polyalkenes from which the substituents are derived, it is understood that these more preferred properties of the succinic acylating agents are intended to be understood, both as unique and dependent. It should be pointed out. These are, in a sense, considered to be independent of the following: for example, even though a minimum of 1.4 or 1.5 succinic groups per equivalent of substituent is preferred, it is n or w / n Not tied to more favorable values. They are considered in some sense to depend on: for example, 1.4 or
When the suitability of a minimum of 1.5 succinic groups is combined with the more preferred values of n and / or w / n,
This preferred combination effectively represents an even more preferred embodiment of the present invention. Therefore, the various parameters are considered isolated with respect to the particular parameter discussed. However, these parameters can also be combined with other parameters to further confirm their preference. This same concept relates to the description of more preferred values, ranges, ratios, reactants, etc.
If different meanings are not explicitly provided or are not apparent, they are intended to apply throughout this specification.

In one embodiment, when n of the polyalkene is at the lower end of this range (eg, about 1300), the ratio of succinic acid groups to substituents from which the polyalkene is derived in the acylating agent is: Preferably, for example, n is 1500
Higher than the ratio of Conversely, when the polyalkene n is higher (eg, 2000), the ratio is lower than when the polyalkene n is 1500, for example.

The polyalkenes from which the substituents are derived are homopolymers and mixed weights of polymerizable olefin monomers, which have from 2 to about 16 carbon atoms, usually from 2 to about 6 carbon atoms. It is united. The mixed polymer is a polymer in which two or more olefin monomers are co-polymerized by known conventional methods to form the following polyalkene: The polyalkene has, within its structure,
It has units derived from each of the two or more olefin monomers. Thus, "mixed polymer" as used herein includes copolymers, terpolymers, quaternary copolymers, and the like. As will be apparent to those skilled in the art, the polyalkene from which the substituent is derived is often commonly referred to as a "polyolefin."

The olefin monomers from which the polyalkenes are derived are polymerizable olefin monomers characterized by the presence of one or more ethylenically unsaturated groups (ie,> C = C <):
Monoolefinic monomers (eg, ethylene, propylene, butene-1, isobutene, and octene-1)
Or a polyolefinic monomer (typically a diolefinic monomer; for example, butadiene-1,3 and isoprene).

These olefinic monomers are usually polymerizable terminal olefins (ie, in the structure, the group> C =
Olefins characterized by the presence of CH ₂ ).
However, polymerizable internal olefin monomers (sometimes referred to in the literature as intermediate olefins; they are characterized in their structure by the presence of the following groups) also form polyalkenes: Can be used to: When internal olefin monomers are used, they are usually used with terminal olefins to produce mixed polymers, polyalkenes. For the purposes of this invention, when a particular polymerized olefin monomer can be classified as both a terminal olefin and an internal olefin, it is considered a terminal olefin. Therefore, 1,3-pentadiene (ie, piperylene) is considered a terminal olefin for the purposes of this invention.

Some of the substituted succinic acylating agents (B-1) useful in preparing the carboxylic acid ester (B) include:
Known in the art, for example, U.S. Pat.
It is described in No. 5. These disclosures are set forth herein in this regard. The acylating agents described in the '435 patent include polyalkenes, which comprise from about 1300 to about 50
00n value, and a w / n value of about 1.5 to about 4)
Is characterized as containing a substituent derived from

Aliphatic hydrocarbon polyalkenes free of aromatic and cycloaliphatic groups generally have certain advantages. Of this general preference, further preference is given to polyalkenes derived from the group consisting of: the group consisting of the monohydric weight of terminal hydrocarbon olefins having from 2 to about 16 carbon atoms. It consists of coalesced and mixed polymers. This further preference is limited by the following conditions: a mixed polymer of terminal olefins is usually preferred, but about 40% derived from internal olefins having up to about 16 carbon atoms. It is a condition that mixed polymers containing any of the above polymer units arbitrarily belong to a preferable group. A more preferred class of polyalkene is a polyalkene selected from the group consisting of: this group has a terminal olefin having from 2 to about 6 carbon atoms, more preferably having 2 to 4 carbon atoms. It comprises a homopolymer and a mixed polymer of terminal olefins. However, another more preferred class of polyalkenes is the latter more preferred polyalkenes. The polyalkene is a polyalkene optionally containing up to about 25% polymer units, derived from internal olefins having up to about 6 carbon atoms.

Obviously, a polyalkene as described above (this is
meets various criteria for n and w / n)
Is within the skill of the art and is not part of the present invention. Techniques readily apparent to those skilled in the art include controlling the polymerization temperature, adjusting the amount and type of polymerization initiator and / or catalyst, using chain terminating groups in the polymerization process, and the like. You. Other conventional methods (eg, stripping very light fragments (including vacuum stripping), and / or oxidatively or mechanically decomposing high molecular weight polyalkenes to produce low molecular weight polyalkenes) Can also be used.

In preparing the substituted succinic acylating agent of the present invention,
One or more of the above polyalkenes is subjected to a reaction with one or more acidic reactants selected from the group consisting of: a maleic acid reactant or fumal of the general formula Consisting of the acid reactant: X (O) C-CH = CH-C (O) X '(IV) wherein X and X' have been previously defined in Formula I.

Preferably, the maleic and fumaric reactants are one or more compounds corresponding to the formula: RC (O) -CH = CH-C (O) R '(V) where , R and R 'are the same as previously defined in Formula II herein.

Typically, the maleic or fumaric acid reactant is maleic acid, fumaric acid, maleic anhydride, or a mixture of two or more thereof. This maleic acid reactant is usually preferred over the fumaric acid reactant. The former are readily available and, in general, readily react with polyalkenes (or their derivatives) to prepare the substituted succinic acylating agents of the invention. Particularly preferred reactants are maleic acid, maleic anhydride, and mixtures thereof. For reasons of availability and ease of reaction, maleic anhydride is usually used.

Examples of patents describing various methods for preparing useful acylating agents include U.S. Patent No. 3,235,707 (Rens
e); 3,219,666 (Norman et al.); 3,231,587 (Rense);
3,912,764 (Palmer); 4,110,349 (Cohen); and
4,234,435 (Meinhardt et al.); And British Patent No. 1,44.
No. 0,219 is included. The contents of these patents are set forth here.

For convenience and brevity, the term "maleic acid reactant" is often used herein. As used, the term refers to acidic reactants selected from the maleic and fumaric acid reactants corresponding to Formulas (IV) and (V) above, including, but not limited to, those reactants. It is to be understood that mixtures are encompassed).

The acylating reagent described above is an intermediate in a method for preparing the carboxylic acid derivative composition (B). The method includes one or more acylating reagents (B-
1) and at least one amino compound (B-2), which is characterized by the presence of at least one HN <group in its structure.

Amino compound (B-2) characterized by the presence of at least one HN <group in its structure,
It can be a monoamine compound or a polyamine compound.
A mixture of two or more amino compounds is reacted with one or more acylating reagents of the invention to form
Can be used. Preferably, the amino compound contains at least one primary amino group (i.e., -NH _2), more preferably, it contains the amine is a polyamine (in particular, at least two -NH- groups Polyamine)
It is. Either or both of the amines are primary or secondary amines. The amine can be an aliphatic amine, a cycloaliphatic amine, an aromatic amine, or a heterocyclic amine. The polyamine not only results in a carboxylic acid derivative composition, which is usually more effective as a dispersing / cleaning additive compared to a derivative composition derived from a monoamine, but also These more preferred polyamines result in carboxylic acid derivative compositions that exhibit more pronounced VI improving properties.

Among the more preferred amines are the alkylene polyamines, including the polyalkylene polyamines. The alkylene polyamines include those according to the formula: Wherein n is 1 to about 10; each R ³ is independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group or an amino-substituted hydrocarbyl group, which have up to about 30 atoms. Or two R ³ on different nitrogen atoms may be joined together to form a U group; provided that at least one R ³ group is hydrogen;
Is an alkylene group having from about 2 to about 10 carbon atoms, preferably U is ethylene or propylene. Alkylene polyamines are particularly preferred, where each R ³ is hydrogen or an amino-substituted hydrocarbyl group. Ethylene polyamines and mixtures of ethylene polyamines are most preferred. Usually, n is about 2 to about 7
Has an average value of Such alkylene polyamines include methylene polyamine, ethylene polyamine, butylene polyamine, propylene polyamine, pentylene polyamine, hexylene polyamine, heptylene polyamine and the like. Also included are high molecular weight analogs of such amines, and related aminoalkyl-substituted piperazines.

In preparing the carboxylic acid derivative composition (B), useful alkylene polyamines include ethylenediamine, triethylenetetramine, propylenediamine, trimethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, di (heptamethylene). Diamine) triamine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, di (trimethylene) -triamine, N- (2-aminoethyl) piperazine, 1,4-bis (2-aminoethyl) piperazine , And the like. Higher homologs, such as those obtained by condensation of two or more of the above alkylene amines,
Useful as well as mixtures of any two or more of the above polyamines.

Ethylene polyamines, such as those mentioned above, are particularly useful for their price and effectiveness.
Such polyamines are known under the title "Diamines and higher amines" in the Chemical Technical Dictionary (2nd edition, Kirk and O
thmer, Vol. 7, p.27-39, Interscience Publishing, John
Wiley and Sons, 1965), the contents of which are set forth herein with respect to the disclosure of useful polyamines. Such compounds are most conveniently prepared by reacting an alkylene chloride with ammonia, or by reacting ethyleneimine with a ring-opening reagent such as ammonia. By these reactions,
A complex mixture of alkylene polyamines is obtained, including cyclic condensation products such as piperazine. This mixture is particularly useful when preparing the carboxylic acid derivative (B) of the present invention. On the other hand, completely satisfactory products are also obtained by using pure alkylene polyamines.

Another useful type of polyamine mixture is a mixture obtained by stripping the above polyamine mixture. In this case, the low molecular weight polyamine and volatile impurities are removed from the alkylene polyamine mixture,
A residue often called "polyamine bottoms" remains. Generally, alkylene polyamine bottoms are about 200
Substances boiling below ℃ can be characterized as having not more than 2%, usually not more than 1% (by weight). In the case of ethylene polyamine bottoms, which are readily available and have been found to be quite useful, the bottoms should have a total of no more than about 2% (by weight) of diethylenetriamine (DETA) or Triethylenetetramine (TETA). A typical sample of ethylene polyamine bottoms, such as that obtained from Dow Chemical Company (Freeport, Texas) (this is named "E-100")
Has a specific gravity of 1.0168 at 15.6 ° C., a nitrogen percentage of 33.15% by weight, and a viscosity of 121 centistokes at 40 ° C. Gas chromatography analysis of such a sample
This is about 0.93% "light end" (mostly DA
TE), 0.72% TETA, 21.74% tetraethylenepentamine, and 76.61% and higher pentaethylenehexamine (by weight). These alkylene polyamine bottoms include cyclic condensation products (eg, piperazine) and higher analogs such as ethylene triamine and triethylene tetramine.

If the amino reactant consists essentially of alkylene polyamine bottoms, these alkylene polyamine bottoms may be alone subjected to the reaction with the acylating agent. Or, these are other amines and polyamines,
Or it can be used with alcohols or mixtures thereof. In the latter case, the at least one amino reactant contains alkylene polyamine bottoms.

According to these inventions, other polyamines that can be subjected to a reaction with the acylating agent (B-1) are described, for example, in US Pat.
Nos. 219,666 and 4,234,435. The contents of these patents are set forth herein with reference to the disclosure of amines, which can be reacted with the acylating agents described above to form the carboxylic acid derivatives (B) of the present invention. .

The carboxylic acid derivative composition (B) produced from the acylating reagent (B-1) and the amino compound (B-2) described above contains an acylated amine. The amine includes amine salts, amides, imides and imidazolines, as well as mixtures thereof. To prepare a carboxylic acid derivative from an acylating reagent and an amino compound, the one or more acylating reagents and the one or more amino compounds should be at about 80 ° C. to the decomposition point (where the decomposition point Is optionally heated in the presence of a liquid, substantially inert organic liquid solvent / diluent, at a temperature in the range up to (as previously defined).
However, the compound is typically heated to a temperature ranging from about 100 ° C to about 300 ° C, with 300 ° C not exceeding this decomposition point. Temperatures from about 125 ° C to about 250 ° C are typically used. The acylating reagent and the amino compound are subjected to the reaction in an amount sufficient to obtain from 1/2 equivalent to 2 mol of the amino compound per equivalent of the acylating reagent.

This acylating reagent (B-1) can be reacted with an amino compound (B-2) in the same manner as a prior art high molecular weight acylating agent is reacted with an amine,
The disclosures of U.S. Patent Nos. 3,172,892; 3,219,666; 3,272,746; and 4,234,435 are set forth herein with respect to methods applicable to the reaction of an acylating reagent with an amino compound as described above.

It has generally been found that the acylating reagents need to be reacted with polyfunctional reactants in order to produce carboxylic acid derivative compositions that exhibit the potential for improving the viscosity index. For example, polyamines having two or more primary and / or secondary amino groups are more preferred. Obviously, however, not all of the amino compounds that are subjected to the reaction with the acylating reagent need be polyfunctional. Therefore, a combination of monofunctional and polyfunctional amino compounds is used.

In some embodiments, the acylating agent is an acylating agent 1
The reaction is carried out with about 0.70 equivalents to no more than 1 equivalent (eg, about 0.95 equivalents) of the amino compound per equivalent. The lower limit, based on the equivalents of the amino compound, can be from 0.75 equivalents or just 0.80 equivalents to about 0.90 equivalents or 0.95 equivalents per equivalent of acylating agent. Therefore, the acylating agent (B) for the amino compound (B-2)
A narrower range of equivalents for -1) can be from about 0.70 equivalents to about 0.90 equivalents, or from about 0.75 equivalents to about 0.90 equivalents, or from about 0.75 equivalents to about 0.85 equivalents. At least in some situations, the equivalent of the amino compound is about 0.75 equivalents per equivalent of the acylating agent.
At or below that, it is clear that the effect of the carboxylic acid derivative as a dispersant is reduced. In certain embodiments, the relative amounts of acylating agent and amine are such that the carboxylic acid derivative preferably does not contain free carboxyl groups.

In another embodiment, the acylating agent is acylating agent 1
About 1.0 equivalent to about 1.1 equivalents, or up to about 1.5 equivalents, of amino compound per equivalent is provided for the reaction.

Within the above range, the amount of amine compound (B-2) subjected to the reaction with the acylating agent (B-1) may also depend in part on the number and type of nitrogen atoms present. For example, in order to provide for reaction with certain acylating agents, polyamine containing one or more -NH ₂ groups, -NH ₂ group with a nitrogen atom of the same number or absent less Lesser amounts are required than polyamines. One -NH
_{The two} groups may be subjected to a reaction with two -COOH groups to form an imide. In this amine compound, if only a secondary nitrogen is present, each -NH group can only be reacted with one -COOH group. Therefore, within the scope of the above, are reacted with the acylating agent the amount of polyamine carboxylic acid derivative capable of forming the present invention, the polyamine (i.e., -NH _2,> NH, and> N It can be easily determined by considering the number and type of nitrogen atoms in-).

In addition to the relative amounts of the acylating agent and the amino compound used to form the carboxylic acid derivative composition (B), another important feature of the carboxylic acid derivative composition used in the present invention is the polyalkylene derivative. N value and
w / n values, and that in the acylating agent there is an average of at least 1.3 succinic groups for each equivalent of substituent. When all of these characteristics are present in the carboxylic acid derivative composition (B), the lubricating oil composition of the present invention exhibits new and improved properties. The lubricating oil composition is characterized by improved performance of the internal combustion engine.

With respect to the equivalent weight of the substituent present in the acylating agent,
The ratio of succinic groups can be determined from the number of saponifications of the mixture subjected to the reaction. This saponification number was corrected to account for unreacted polyalkene present in the reaction mixture at the end of the reaction, which is generally indicated in the following examples as filtrate or residue. You. The formula for calculating this ratio from the number of saponifications is: The corrected number of saponifications is obtained by dividing the number of saponifications by the percentage of polyalkene that has been subjected to the reaction. For example, if 10% of the polyalkene is not subjected to the reaction and the filtrate or residue has a saponification number of 95, then the corrected saponification number is 95 divided by 0.90, or 105.5.

The preparation of this acylating agent is illustrated in Examples 1-3 below. The preparation of the carboxylic acid derivative composition (B) is exemplified by the following Examples B-1 to B-26. In the following examples, and elsewhere in this specification and claims, all percentages and parts are by weight, temperatures are in degrees Celsius, and pressures are high unless otherwise indicated. Atmospheric pressure.

Acylating agent: Example 1 510 parts (0.28 mol) of polyisobutene (n = 1845; w = 5325) and 59 parts (0.59 mol) of maleic anhydride
Is heated to 110 ° C. The mixture is heated to 190 ° C. for 7 hours. During this time, 43 parts of gaseous chlorine (0.6 parts)
Mol) is added subsurface. At 190-192 ° C, an additional 11 parts of chlorine (0.16 mol) are added over 3.5 hours. The reaction mixture is heated at 190-193 ° C. for 1 hour while blowing nitrogen.
By heating for 0 hours, volatile components are removed therefrom. This residue is the desired polyisobutene-substituted succinic acylating agent, which was determined by ASTM method D-94,
With a saponification equivalent number of 87).

Example 2 A mixture of 1000 parts (0.495 mol) of polyisobutene (n = 2020; w = 6049) and 115 parts (1.17 mol) of maleic anhydride is heated to 110 ° C. This mixture is
Heat to 184 ° C. for 6 hours. During this time, 85 parts (1.2 mol) of gaseous chlorine are added subsurface. At 184-189 ° C., an additional 59 parts (0.83 mol) of chlorine are added over 4 hours.
The reaction mixture is heated at 186-190 ° C. for 2
The volatile components are removed therefrom by heating for 6 hours. This residue is the desired polyisobutene-substituted succinic acylating agent, which was determined by ASTM method D-94,
With a saponification equivalent number of 87).

Example 3 Polyisobutene chloride (prepared by adding 251 parts of gaseous chlorine to 3000 parts of polyisobutene (n = 1696; w = 6594) at 84 ° C. over 4.66 hours) and anhydrous A mixture of 345 parts of maleic acid is heated to 200 ° C. over 0.5 hours. The reaction mixture is
Maintain at 6.degree. C. for 6.33 hours, remove volatile components at 210.degree. C. under vacuum and filter. The filtrate is the desired polyisobutene-substituted succinic acylating agent, which has a saponification equivalent number of 94 as determined by ASTM method D-94.

Carboxylic acid derivative composition (B): Example B-1 10.2 parts (0.25 equivalent) of a commercially available mixture of ethylene polyamines
(Which has from about 3 to about 10 nitrogen atoms per molecule) are combined with 113 parts of mineral oil and 161 of the substituted succinic acylating agent (which was prepared in Example 1 at 138 ° C). A mixture is prepared by adding to parts (0.25 equivalents). The reaction mixture is heated to 150 ° C. for 2 hours and the volatile components are removed by blowing nitrogen. Filtration of the reaction mixture gives a filtrate as an oil solution of the desired product.

Example B-2 57 parts (1.38 equivalents) of a commercial mixture of ethylene polyamines
(Which has about 3 to about 10 nitrogen atoms per molecule), 1067 parts mineral oil and a substituted succinic acylating agent (which was prepared in Example 2 at 140-145 ° C) Of 893
A mixture is prepared by adding to parts (1.38 equivalents). The reaction mixture is heated to 155 ° C. for 3 hours and the volatile components are removed by blowing nitrogen. Filtration of the reaction mixture gives a filtrate as an oil solution of the desired product.

Example B-3 A mixture of 1132 parts mineral oil and 709 parts (1.2 equivalents) of the substituted succinic acylating agent prepared as in Example 1 is prepared. A solution of 56.8 parts (1.32 equivalents) of piperazine in 200 parts of water is slowly added to the above mixture from the dropping funnel at 130-140 ° C. over approximately 4 hours. While removing water,
Continue heating to 160 ° C. The mixture is maintained at 160-165 ° C. for 1 hour and cooled overnight. 160 of this mixture
After reheating to 0 ° C., the mixture is maintained at this temperature for 4 hours. Mineral oil (270 parts) is added and the mixture is filtered at 150 ° C. with a filter aid. The filtrate is the desired product (65% oil) containing 0.65% nitrogen (0.86% theory).

Example B-4 A mixture of 1968 parts of mineral oil and 1508 parts (2.5 equivalents) of the substituted succinic acylating agent prepared as in Example 1 was charged with 145 parts.
Heat to ° C. In contrast, 125.6 parts (3.0 equivalents) of a commercially available mixture of ethylene polyamines as used in Example B-1 were added while maintaining the reaction temperature at 145-150 ° C.
Add over time. The reaction mixture is stirred at 150-152 ° C. for 5.5 hours while blowing with nitrogen. The mixture is filtered at 150 ° C. with a filter aid. The filtrate is an oil solution (55% oil) of the desired product containing 1.20% nitrogen (theory 1.17).

Example B-5 4082 parts of a mineral oil and 250.8 parts (6.24 equivalents) of a commercially available mixture of ethylene polyamines of the type utilized in Example B-1 are heated to 110 ° C. On the contrary,
Substituted succinic acylating agents 31 prepared as in Example 1
36 parts (5.2 equivalents) are added over 2 hours. During the addition, the temperature is maintained at 110-120 ° C while blowing with nitrogen. When all the amine has been added, the mixture is added to 16
Heat to 0 ° C. and maintain at this temperature for about 6.5 hours while removing water. The mixture is filtered at 140 ° C. with a filter aid. The filtrate is an oil solution (55% oil) of the desired product containing 1.17% nitrogen (theory 1.18).

Example B-6 A mixture of 4158 parts mineral oil and 3136 parts (5.2 equivalents) of the substituted succinic acylating agent prepared in Example 1 is heated to 140 ° C. In contrast, 312 parts (7.26 equivalents) of a commercially available mixture of ethylene polyamines as used in Example B-1 are added over 1 hour, increasing the temperature to 140-150 ° C. The mixture is maintained at 150 ° C. for 2 hours while blowing with nitrogen and at 160 ° C. for 3 hours. The mixture is filtered at 140 ° C. with a filter aid. The filtrate is an oil solution (55% oil) of the desired product containing 1.44% nitrogen (theoretical 1.34).

Example B-7 A mixture of 4053 parts mineral oil and 287 parts (7.14 equivalents) of a commercial mixture of ethylene polyamines as used in Example B-1 is heated to 110 ° C. In contrast, 3075 parts of the substituted succinic acylating agent prepared as in Example 1 (5.
1 eq.) Is added over 1 hour while maintaining the temperature at about 110 ° C. The mixture is heated to 160 ° C. for 2 hours and maintained at this temperature for a further 4 hours.
Then, the reaction mixture is filtered at 150 ° C. with a filter aid. The filtrate is an oil solution (55% oil) of the desired product containing 1.33% nitrogen (theory 1.36).

Example B-8 A mixture of 1503 parts mineral oil and 1220 parts (2 equivalents) of the substituted succinic acylating agent prepared in Example 1 is heated to 110 ° C. In contrast, 120 parts (3 equivalents) of a commercially available mixture of ethylene polyamines of the type used in Example B-1
Is added over about 50 minutes. The reaction mixture is
Stir at 0 ° C. for another 30 minutes, then raise the temperature,
Maintain at about 151 ° C. for 4 hours. A filter aid is added and the mixture is filtered. The filtrate contains 1.44% nitrogen (theoretical 1.
49) is an oil solution of the desired product (53.2% oil).

Example B-9 A mixture of 3111 parts of mineral oil and 844 parts (21 equivalents) of a commercial mixture of ethylene polyamines as used in Example B-1 is heated to 140C. To this, 3885 parts (7.0 equivalents) of the substituted succinic acylating agent prepared as in Example 1 are added over about 1.75 hours while increasing the temperature to about 150 ° C. While blowing in nitrogen, the mixture is
Maintain at 0-155 ° C. for about 6 hours, then filter at 130 ° C. with a filter aid. The filtrate is 3.5% nitrogen (3.7% theoretical).
8) is an oil solution of the desired product (40% oil).

Example B-10 18.2 parts (0.433 equivalents) of a commercial mixture of ethylene polyamines, which has from about 3 to 10 nitrogen atoms per molecule, are combined with 392 parts mineral oil and a substituted succinic acylating agent, A mixture is prepared by adding 348 parts (prepared at 140 ° C. in Example 2) to 348 parts (0.52 equivalents). The reaction mixture is heated to 150 ° C. in 1.8 hours and the volatile components are removed by blowing nitrogen. The reaction mixture is filtered to give an oil solution of the desired product (55%
The filtrate is obtained as oil).

Example B-11 In a suitably sized flask equipped with a stirrer, nitrogen inlet tube, addition funnel and Dean-Stark trap / cooler, the acylating agent 24 described in Example 3 was added.
Charge a mixture of 83 parts (4.2 equivalents) and 1104 parts of oil. The mixture is heated to 210C. During this time, the mixture is slowly bubbled with nitrogen. Ethylene polyamine bottoms (134 parts, 3.14 equivalents) are added slowly at this temperature over about 1 hour. Temperature, 210 ° C
For 3 hours, then add 3688 parts of oil,
This temperature is reduced to 125 ° C. After storage at 138 ° C. for 17.5 hours, the mixture is filtered through diatomaceous earth to give a 65% oil solution of the desired acylated amine bottoms.

Example B-12 A mixture of 3660 parts (6 equivalents) of the substituted succinic acylating agent prepared in Example 1 and 4664 parts of a diluent oil is prepared at about 110 ° C.
Heat with. In contrast, nitrogen is blown into the mixture. To this mixture is then added over 1 hour a commercial mixture of ethylene polyamine (which contains about 3 to about 10 nitrogen atoms per molecule) and the mixture is kept at 110 ° C. for another 0.5 hour I do. While removing water
After heating at 155 ° C. for 6 hours, the filtrate is added and the reaction mixture is filtered at about 150 ° C. This filtrate is an oil solution of the desired product.

Example B-13 0.8 of the substituted succinic acylating agent prepared in Example 1
The general method of Example B-12 is repeated except that the equivalents have been subjected to a reaction with 0.67 equivalents of a commercially available mixture of ethylene polyamines. The product obtained in this way is an oil solution of the product containing 55% diluent oil.

Example B-14 Example 1 except that the polyamine used in this example is an equivalent of the following alkylene polyamine mixture:
Repeat the general procedure of B-12. This polyamine mixture is
Consists of 80% ethylene polyamine bottoms from Union Carbide, and 20% of a commercially available mixture of ethylene polyamines corresponding to diethylene triamine by empirical formula.
This polyamine mixture is characterized as having an equivalent weight of about 43.3.

Example B-15 The general procedure of Example B-12 is repeated except that the polyamine utilized in this example contains a mixture of 80 parts by weight of ethylene polyamine, commercially available from Dow, and 20 parts by weight of diethylene triamine. . This amine mixture is about
It has an equivalent weight of 41.3.

Example B-16 Substituted Succinic Acylating Agent Prepared as in Example 1
A mixture of 444 parts (0.7 equivalents) and 563 parts mineral oil is prepared and heated to 140 ° C. On the other hand, in the empirical formula,
22.2 parts of an ethylene polyamine mixture corresponding to triethylenetetramine (0.58 equivalents) are added over one hour while maintaining the temperature at 140 ° C. The mixture is blown with nitrogen while heating to 150 ° C. and maintained at this temperature for 4 hours while removing water. This mixture is then
Filter at about 135 ° C with a filter aid. This filtrate is about 55%
Oil solution of the desired product containing mineral oil.

Example B-17 Substituted Succinic Acylating Agent Prepared as in Example 1
A mixture of 422 parts (0.7 equivalents) and 188 parts mineral oil is prepared and heated to 210 ° C. In contrast, 22.1 parts (0.2%) of a commercial mixture of ethylene polyamine bottoms from Dow.
53 equivalents) is added over 1 hour while blowing with nitrogen. The temperature is then raised to about 210-216 ° C and maintained at this temperature for 3 hours. Mineral oil (625 parts) is added and the mixture is maintained at 135 ° C. for about 17 hours. On the other hand, the mixture is filtered. The filtrate is an oil solution of the desired product (65% oil).

Example B-18 Example B- except that the polyamine used in this example is a commercially available mixture of ethylene polyamines having from about 3 to about 10 nitrogen atoms per molecule (42 equivalents).
Repeat the 17 general methods.

Example B-19 414 of substituted succinic acylating agent prepared in Example 1
Parts (0.71 equivalents) and a mixture of 183 parts mineral oil are prepared. The mixture is heated to 210C. On the other hand, ethylene polyamine (which is about 3 to about
20.5 parts (0.49 parts) of a commercial mixture having 10 nitrogen atoms)
) Is added over about 1 hour while increasing the temperature to 210-217 ° C. The reaction mixture is maintained at this temperature for 3 hours while blowing with nitrogen. Add 612 parts of mineral oil. The mixture is allowed to stand at 135-145 ° C. for about one hour and
Maintain at 17 ° C for 17 hours. The mixture is filtered while warm. The filtrate is an oil solution of the desired product (65% oil).

Example B-20 Substituted Succinic Acylating Agent Prepared in Example 1
Parts (0.71 equivalents), and a mixture of 184 parts mineral oil,
Heat to about 80 ° C. In contrast, 22.4 parts of melamine (0.
534 equivalents). This mixture is added to 160
Heat to 0 ° C. and maintain at this temperature for 5 hours. After cooling overnight, the mixture is heated to 170 ° C. over 2.5 hours and to 215 ° C. over 1.5 hours. The mixture is maintained at about 215 ° C for about 4 hours and at about 220 ° C for 6 hours. After cooling overnight, the reaction mixture is filtered at 150 ° C. with a filter aid. The filtrate is an oil solution of the desired product (30% mineral oil).

Example B-21 A mixture of 414 parts (0.71 equivalents) of the substituted acylating agent prepared in Example 1 and 184 parts of mineral oil is heated to 210 ° C. In contrast, empirical formulas have shown that 21 parts (0.53 equivalents) of a commercially available mixture of ethylene polyamines corresponding to tetraethylene pentamine were added to 0.5 parts while maintaining the temperature at about 210-217 ° C.
Add over time. As soon as the addition of the polyamine was completed, the mixture was brought to 217 ° C. while blowing with nitrogen.
For 3 hours. Mineral oil (613 parts) is added, the mixture is maintained at about 135 ° C. for 17 hours and filtered. The filtrate is an oil solution of the desired product (65% mineral oil).

Example B-22 414 parts of the substituted acylating agent prepared in Example 1 (0.71
Eq.) And 183 parts of mineral oil are prepared and heated to 210 ° C. In contrast, 18.3 parts (0.44 equivalents) of ethyleneamine bottoms (Dow) were blown in with nitrogen,
Add over 1 hour. This mixture is left for about 15 minutes
Heat to 210-217 ° C and maintain at this temperature for 3 hours.
An additional 608 parts of mineral oil are added and the mixture is allowed
Maintain time. The mixture is filtered at 135 ° C. with a filter aid. The filtrate is an oil solution of the desired product (65% oil).

Example B-23 Ethyleneamine bottoms are converted to ethylenepolyamine, which has about 3 to 10 nitrogen atoms per molecule
Example B-
Repeat the 22 general methods.

Example B-24 A mixture of 422 parts (0.70 equivalents) of the substituted acylating agent prepared in Example 1 and 190 parts mineral oil is heated to 210 ° C. In contrast, ethyleneamine bottoms (Dow)
26.75 parts (0.636 equivalents) are added over 1 hour while blowing with nitrogen. After adding all of the ethyleneamine,
The mixture is maintained at 210-215 ° C. for about 4 hours. To this mixture, 632 parts of mineral oil are added with stirring. The mixture is maintained at 135 ° C. for 17 hours and filtered with a filter aid.
The filtrate is an oil solution of the desired product (65% oil)
It is.

Example B-25 468 of substituted succinic acylating agents prepared in Example 1
Parts (0.8 equivalents) and 908.1 parts of mineral oil at 142 ° C.
Heat until To this, 28.63 parts (0.7 equivalents) of ethyleneamine bottoms (Dow) are added over 1.5-2 hours. The mixture is stirred at about 142 ° C. for a further 4 hours and filtered. The filtrate is an oil solution of the desired product (65% oil).

Example B-26 A mixture of 2653 parts of the substituted acylating agent prepared in Example 1 and 1186 parts of mineral oil is heated to 210 ° C. To this, 154 parts of ethyleneamine bottoms (Dow) are added over 1.5 hours while maintaining the temperature between 210-215 ° C. The mixture is maintained at 215-220 ° C. for about 6 hours. At 210 ° C., mineral oil (3953 parts) was added and the mixture was
Stir for 17 hours at 28-135 ° C. while blowing nitrogen. The mixture is filtered while warming with a filter aid. The filtrate is an oil solution of the desired product (65% oil).

(C) Metal salt of dihydrocarbyl phosphorodithioic acid The lubricating oil composition of the present invention comprises from about 0.05% to about 5% by weight of a mixture of metal salts of dihydrocarbyl phosphorodithioic acid.
Contained in. Here, in at least one dihydrocarbyl phosphorodithioic acid, one of the hydrocarbyl groups (C-1) is an isopropyl group or a secondary butyl group, and the other hydrocarbyl group (C-2) has at least 5
Contains carbon atoms. At least about 20 mole percent of all hydrocarbyl groups present in (C) are isopropyl groups, secondary butyl groups, or mixtures thereof. However, this lubricating oil composition contains about 2.5% of the component (B).
When contained in an amount not to exceed weight percent, at least about 25 mole percent of the hydrocarbyl groups in (C) are isopropyl groups, secondary butyl groups, or mixtures thereof.

In another embodiment, the lubricating oil composition contains a mixture of metal salts of dihydrocarbyl phosphorodithioic acid.
Here, in at least one of the phosphorodithioic acids,
One of the hydrocarbyl groups (C-1) is an isopropyl group or a secondary butyl group, and the other hydrocarbyl group (C-2) contains at least 5 carbon atoms. The lubricating oil composition contains at least about 0.05% by weight of the isopropyl groups, secondary butyl groups or mixtures thereof derived from (C). However, when the lubricating oil composition contains about 2.5% by weight of (B), the oil composition will have at least about 0.06% by weight of isopropyl and / or secondary butyl groups derived from (C). %
It contains. In a further embodiment, the lubricating oil composition of the present invention may contain at least 0.08% by weight of the isopropyl and / or secondary butyl groups derived from (C).

Can be added in or to this oil (C)
The amount of isopropyl or secondary butyl groups derived from can be calculated using the following formula: 43 ^* is the formula weight of the isopropyl group.

57 ^* is the formula weight of the secondary butyl group.

31 ^* is the atomic weight of phosphorus.

The metal salt of dihydrocarbyl phosphorodithioic acid contained in the mixture of (C) can generally be characterized by the following formula: Here, R ¹ and R ² are each independently a hydrocarbyl group containing at least 3 carbon atoms.
M is a metal and n is an integer equal to the valency of M.

In at least one salt present in this mixture (C), R ¹ is an isobutyl or secondary butyl group, and R ² is a hydrocarbyl group containing at least 5 carbon atoms. At least 20 mole percent of all hydrocarbyl groups present in the mixture of (C) are isopropyl groups, secondary butyl groups or mixtures thereof.

In the dithiophosphates of formula VII, the hydrocarbyl groups R ¹ and R ² (which are not isopropyl or secondary butyl) are substituted with alkyl, cycloalkyl, aralkyl or alkaryl, or analogous structures. It can be a substantial hydrocarbon group. By “substantially hydrocarbon”, this is meant a hydrocarbon containing substituents (eg, ether, ester, nitro or halogen) that do not significantly alter the hydrocarbon nature of the group.

Exemplary alkyl groups include isobutyl, n-butyl, se.
c-butyl, various amyl groups, n-hexyl, methyl isobutyl, carvinyl, heptyl, 2-ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl,
Includes decyl, dodecyl, tridecyl and the like. Exemplary alkylphenyl groups include butylphenyl, amylphenyl, heptylphenyl, dodecylphenyl, and the like. Cycloalkyl groups are also useful. These mainly include cyclohexyl and lower alkylcyclohexyl groups. Many substituted hydrocarbon groups, such as chloropentyl, dichlorophenyl, and dichlorodecyl, can also be used.

Phosphorodithioic acids from which metal salts useful in this invention can be prepared are known. Dihydrocarbyl phosphorodithioic acids and metal salts, and methods for preparing such acids and salts, are described, for example, in U.S. Pat.
8,154; and 4,417,990. The contents of these patents are set forth herein with respect to such disclosure.

The phosphorodithioic acid is prepared by reacting phosphorus pentasulfide with an alcohol, phenol, a mixture of alcohols, or a mixture of alcohol and phenol. This reaction involves 4 moles of alcohol or phenol per mole of phosphorus pentasulfide. The reaction can be performed at a temperature ranging from about 50C to about 200C. Thus, the preparation of 0,0-di-n-hexyl phosphorodithioic acid involves the reaction of phosphorus pentasulfide with 4 moles of n-hexyl alcohol at about 100 ° C for about 2 hours. Hydrogen sulfide is liberated and the residue is the acid defined. The preparation of the metal salt of the acid can be carried out by reaction with a metal oxide. Simply mixing and heating these two reactants is
Enough to cause a reaction. The product obtained is sufficiently pure for the present invention.

Metal salts of dihydrocarbyl dithiophosphates useful in this invention include Group I metals, Group II metals, aluminum,
These salts include lead, tin, molybdenum, manganese, cobalt and nickel. Group II metals, aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel and copper are among the more preferred metals. Zinc and copper are particularly useful metals. Examples of metal compounds that can be reacted with this acid to form a metal salt include lithium oxide, lithium hydroxide, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate,
Silver oxide, magnesium oxide, magnesium hydroxide, calcium oxide, zinc hydroxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, barium oxide, aluminum oxide, iron carnbonate, copper hydroxide,
Lead hydroxide, tin butyrate, cobalt hydroxide, nickel hydroxide, nickel carbonate and the like are included.

In some cases, certain components (eg, small amounts of metal acetate,
Or acetic acid combined with a metal reactant) facilitates the reaction, resulting in an improved product. For example, the use of up to about 5% zinc acetate in combination with the required amount of zinc oxide promotes the formation of zinc phosphorodithioate.

Particularly useful metal phosphorodithioates can be prepared from phosphorodithioic acids. The phosphorodithioic acid is prepared in turn by reacting phosphorus pentasulfide with an alcohol mixture. Furthermore, by using such a mixture,
Inexpensive alcohols that do not by themselves produce oil-soluble phosphorodithioic acids can be used. Therefore, a mixture of isopropyl alcohol and hexyl alcohol can be used to produce a very useful oil-soluble metal phosphorodithioate. For the same reason, the mixture of phosphorodithioic acids is subjected to a reaction with a metal compound,
Forms inexpensive oil-soluble salts.

The mixture of alcohols can be a mixture of different primary alcohols, a mixture of different secondary alcohols, or a mixture of primary and secondary alcohols.
Examples of useful mixtures include: isopropyl alcohol and isoamyl alcohol; isopropyl alcohol and isooctyl alcohol; secondary butyl alcohol and isooctyl alcohol; n-butanol and n-octanol; n-pentanol and 2-ethyl-1-hexanol; isobutyl alcohol and n-hexanol; isobutyl alcohol and isoamyl alcohol; isopropanol and 2-methyl-4-pentanol; isopropyl alcohol and sec-butyl alcohol; isopropanol and isooctyl alcohol; −
Hexyl alcohol and isooctyl alcohol.

As mentioned above and in the appended claims, at least one phosphorodithioate salt included in the mixture (C) comprises one hydrocarbyl group (C-1) which is an isopropyl group or a secondary butyl group. Is characterized as containing. Other hydrocarbyl groups (C-2) contain at least 5 carbon atoms. These acids are prepared from a mixture of the corresponding alcohols.

The alcohol mixture utilized in preparing the phosphorodithioic acid required by the present invention may be a mixture of isopropyl alcohol, a mixture of secondary butyl alcohols or a mixture of isopropyl alcohol and secondary butyl alcohol, and at least one alcohol. Species of primary or aliphatic alcohols, which contain about 5 to 13 carbon atoms. In particular, the alcohol mixture contains at least 20, 25 or 30 mole percent of isopropyl alcohol and / or secondary butyl alcohol, and generally comprises from about 20 mole% to about 90 mole% of isopropyl alcohol or secondary butyl alcohol. It contains. In certain more preferred embodiments, the alcohol mixture contains from about 30 mole% to about 60 mole% isopropyl alcohol, with the balance being one or more primary aliphatic alcohols.

Primary alcohols that can be included in this alcohol mixture include n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, 2-ethyl-1-hexyl alcohol, isooctyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, Decyl alcohol and the like. The primary alcohol may also contain various substituents (eg, halogen). Specific examples of useful alcohol mixtures include, for example,
Isopropyl / 2-ethyl-1-hexyl; isopropyl / isooctyl; isopropyl / decyl; isopropyl / dodecyl; and isopropyl / tridecyl. In certain more preferred embodiments, the primary alcohol contains from 6 to about 13 carbon atoms, and the total number of carbon atoms per phosphorus in the required phosphoroditates is at least 9. .

The composition of phosphorodithioic acid obtained by reacting an alcohol mixture (eg, iPrOH and R ² OH) with phosphorus pentasulfide is actually a statistical analysis of three or more phosphorodithioic acids exemplified by the following formula: Is a good mixture: According to the invention, the mixture (wherein the preferred dithiophosphoric acid is a primary dithiophosphoric acid containing one isopropyl or secondary isobutyl group and a primary dithiophosphoric acid group containing at least 5 carbon atoms)
It is more preferable to select the amount of two or more alcohols that are subjected to the reaction with P ₂ S ₅ to obtain an acid (or acids) containing a secondary or secondary alkyl group. . In this statistical mixture, the relative amounts of the three phosphorodithioic acids depend in part on the relative amounts of alcohol in the mixture, steric effects, and the like.

The following examples illustrate the preparation of metal phosphorodithioate prepared from an alcohol mixture, which contains isopropyl alcohol as one of the alcohols.

Example C-1 Alcohol mixture comprising 6 moles of 4-methyl-2
-Containing pentanol and 4 moles of isopropyl alcohol) with phosphorus pentasulfide to prepare a phosphorodithioic acid mixture. The phosphorodithioic acid is then subjected to a reaction with an oil slurry of zinc oxide. The amount of zinc oxide in the slurry is about 1.1 of the theoretical amount required to completely neutralize the phosphorodithioic acid.
08 times. The oil solution of the zinc phosphorodithioate mixture (10% oil) obtained in this way contains 9.5% phosphorus, 20.0% sulfur and 10.5% zinc.

Example C-2 Phosphorodithioic acid mixture by reacting finely divided phosphorus pentasulfide with an alcohol mixture, which contains 11.53 moles (692 parts by weight) of isopropyl alcohol and 7.69 moles (1000 parts by weight) of isooctanol. Is prepared. The phosphorodithioic acid mixture obtained in this way is
It has an acid number of about 178-186, and contains 10.0% phosphorus and 21.0% sulfur.
%. The phosphorodithioic acid mixture is then subjected to a reaction with a zinc oxide oil slurry. The amount of zinc oxide contained in this oil slurry is 1.10 times the theoretical equivalent of the acid number of phosphorodithioic acid. An oil solution of zinc salt prepared in this way contains 12% oil, 8.6
% Phosphorus, 18.5 sulfur, and 9.5% zinc.

Example C-3 Phosphorodithioic acid is prepared by reacting a mixture of 1560 parts (12 mol) of isooctyl alcohol and 180 parts (3 mol) of isopropyl alcohol with 756 parts (3.4 mol) of phosphorus pentasulfide. The reaction heats the alcohol mixture to about 55 ° C. and then raises the reaction temperature to about 60 ° C.
This is done by adding phosphorus pentasulfide over 1.5 hours while maintaining at -75 ° C. After all of the phosphorus pentasulfide has been added, the mixture is heated and stirred at 70-75 ° C. for an additional hour and then filtered through a filter aid.

Zinc oxide (282 parts, 6.87 mol) is charged to the reactor along with 278 parts of mineral oil. The phosphorodithioic acid mixture prepared above (2305 parts, 6.28 mol) was added over 30 minutes
Add to zinc oxide slurry. Heat generation up to 60 ° C is observed. The mixture is then heated to 80 ° C. and kept at this temperature for 3 hours. After removing volatile components to 100 ° C. and 6 mm.Hg., the mixture is filtered twice through a filter aid. This filtrate is the desired oil solution of the zinc salt. This solution is 10% oil, 7.97% zinc (theory 7.40); 7.21
% Phosphorus (theoretical 7.06); and 15.64% (theoretical 14.57)
It contains.

Example C-4 Isopropyl alcohol (396 parts, 6.6 mol) and 1287 parts (9.9 mol) of isooctyl alcohol are charged to a reactor and heated to 59 ° C with stirring. Then, phosphorus pentasulfide (833 parts, 3.75 mol) is added while blowing with nitrogen. The addition of phosphorus pentasulfide is completed in about 2 hours at a reaction temperature between 59-63 ° C. The mixture is then stirred at 45-63 ° C. for about 1.45 hours and filtered.
This filtrate is the desired phosphorodithioic acid mixture.

In a reactor, 312 parts (7.7 equivalents) of zinc oxide and 580 mineral oil
Fill part. While stirring at room temperature, the phosphorodithioic acid mixture prepared above (2287 parts, 6.97 eq) was added to about 1.26
Add over time. Heat generation up to 54 ° C is observed.
The mixture is heated to 78 ° C and maintained at 78-85 ° C for 3 hours. The reaction mixture is removed in vacuo to 100 ° C. and 19 mm.Hg. This residue is filtered with a filter aid. The filtrate is an oil solution of the desired zinc salt (19.2% oil). This solution contains 7.86% zinc, 7.76% phosphorus and
Contains 14.8% sulfur.

Example C-5 Example C-4 except that the molar ratio of isopropyl alcohol to isooctyl alcohol was 1: 1.
Repeat the general method of The product obtained in this way is
Oil solution of zinc phosphorodithioate (10% oil). This solution contains 8.96% zinc, 8.49% phosphorus, and 18.05% sulfur.

Example C-6 Alcohol mixture, which comprises isooctyl alcohol
520 parts (4 moles) and 360 parts (6 moles) of isopropyl alcohol) with 504 parts (2.27 moles) of phosphorus pentasulfide according to the general method of Example C-4.
A phosphorodithioic acid mixture is prepared. 950.8 parts (3.20 mol) of the phosphorodithioic acid mixture prepared above and mineral oil 11
The zinc salt is prepared by reacting 6.3 parts and an oil slurry of 141.5 parts (3.44 mol) of zinc oxide. The product prepared in this way is an oil solution of the desired zinc salt (10% mineral oil). This oil solution contains 9.
Contains 36% zinc, 8.81% phosphorus, and 18.65% sulfur.

Example C-7 A mixture of 520 parts (4 mol) of isooctyl alcohol and 559.8 parts (9.33 mol) of isopropyl alcohol is prepared and heated to 60 ° C. At this point, 672.5 parts (3.03 mol) of phosphorus pentasulfide are added in portions with stirring. The reaction is then maintained at 60-65 ° C. for about 1 hour and filtered. This filtrate is the desired phosphorodithioic acid.

An oil slurry of 188.6 parts (4 moles) of zinc oxide and 144.2 parts of mineral oil is prepared and 1145 parts of the phosphorodithioic acid mixture prepared above are added in portions. During this time, the mixture is maintained at about 70 ° C. After charging all the acid, the mixture is maintained at 80 ° C. for 3 hours. The water is then removed from the reaction mixture to 110 ° C. This residue is filtered with a filter aid. The filtrate is an oil solution of the desired product (10% mineral oil). This oil solution contains 9.99% zinc, 19.55% sulfur, and 9.33% phosphorus.

Example C-8 260 parts (2 mol) of isooctyl alcohol, 480 parts (8 mol) of isopropyl alcohol, and phosphorus pentasulfide 504
Prepare phosphorodithioic acid by the general method of Example C-4 using part (2.27 mol). The phosphorodithioic acid mixture (1094 parts, 3.84 mol) was added over 30 minutes.
Add to the oil slurry, which contains 181 parts zinc oxide (4.41 mole) and 135 parts mineral oil. The mixture is heated to 80 ° C. and maintained at this temperature for 3 hours. After removing volatile components to 100 ° C. and 19 mm.Hg., the mixture is filtered twice with a filter aid. The filtrate is a zinc salt oil solution (10% mineral oil). This oil solution contains 10.06% zinc, 9.04% phosphorus, and 19.2% sulfur.

Additional specific examples of metal phosphorodithioate that may be included in mixture (C) in the lubricating oils of the present invention are listed in the table below. Examples C-9 to C-13 are prepared from an alcohol mixture of the type used to form the required salt. And Examples C-14 to C-20 are prepared from a single alcohol or a mixture of other alcohols. All of this example can be prepared according to the general method of Example C-1.

Another class of phosphorodithioate additive contemplated for use in the lubricating compositions of the present invention includes the above-described adducts of metal phosphorodithioate with epoxides. A metal phosphorodithioate useful in preparing such adducts is most often zinc phosphorodithioate. The epoxide can be an alkylene oxide or an arylalkylene oxide. The arylalkylene oxide includes styrene oxide, p-ethylstyrene oxide, α-methylstyrene oxide,
Exemplified by β-naphthyl-1,1,3-butylene oxide, m-dodecylstyrene oxide, and p-chlorostyrene oxide. This alkylene oxide includes:
Primarily, lower alkylene oxides are included wherein the alkylene group contains eight or fewer carbon atoms. Examples of such lower alkylene oxides include ethylene oxide, propylene oxide, 1,2-butene oxide, trimethylene oxide, tetramethylene oxide, butadiene monoepoxide, 1,2-hexene oxide, and epichlorohydrin. Other epoxides useful herein include, for example, butyl 9,10-epoxystearate, epoxidized soybean oil, epoxidized tung oil, and epoxidized copolymers of styrene and butadiene. .

This adduct is obtained by simply mixing the metal phosphorodithioate and the epoxide. This reaction is usually exothermic and can be carried out within a wide temperature range of about 0 ° C to about 30 ° C. Since the reaction is exothermic, it is best performed by adding one reactant (usually an epoxide) to the other reactant in small portions to manipulate the reaction temperature. The reaction can be performed in a solvent such as benzene, mineral oil, naphtha or n-hexane.

The chemical structure of this adduct is unknown. For this invention, one mole of phosphorodithioate and about 0.25 mole to 5 moles (typically about 0.75 mole) of lower alkylene oxides (especially ethylene oxide and propylene oxide).
Adducts of up to about 0.5 mol, or up to about 0.5 mol) are found to be particularly useful and therefore more preferred.

The preparation of such adducts is more particularly illustrated by the following examples.

Example C-21 Zinc phosphorodithioate 2365 prepared in Example C-2
Parts (3.33 mol) are charged to the reactor. While stirring at room temperature, 38.6 parts (0.67 mol) of propylene oxide are added.
This is accompanied by an exotherm of 24-31 ° C. 80-
Maintain at 90 ° C. for 3 hours, then remove in vacuo to 101 ° C., 7 mm.Hg. This residue is filtered using a filter aid. The filtrate is an oil solution of the desired salt (11.8% oil). This solution contains 17.1% sulfur, 8.17% zinc, and 7.44% phosphorus.

Example C-22 13 parts of propylene oxide (0.5 mole / mole of zinc phosphorodithioate) at 75-85 ° C based on 394 parts (by weight) of zinc dioctyl phosphorodithioate having a phosphorus content of 7% Is added over 20 minutes. The mixture is heated at 82-85 ° C. for 1 hour and filtered. The filtrate (399 parts) contains 6.7% phosphorus, 7.4% zinc, and 4.1%
Of sulfur.

In one embodiment, the mixture of metal dihydrocarbyl phosphorodithioate used as component (C) in the lubricating oil composition of the present invention includes at least one dihydrocarbyl phosphorodithioate salt. Where R ¹ is
An isopropyl or secondary butyl group and the other hydrocarbyl group R ^2, contains at least 5 carbon atoms are derived from primary alcohols. In another embodiment, R ¹ is an isopropyl or secondary butyl group, and R ² is derived from a secondary alcohol containing at least 5 carbon atoms. In a further embodiment, the dihydrocarbyl phosphorodithioic acid used in the preparation of the metal salt is obtained by reacting phosphorus pentasulfide with a mixture of aliphatic alcohols, wherein at least 20 mole percent of the mixture is isopropyl alcohol. ,can get. More generally, such a mixture has at least
Contains 25 mole percent or 30 mole percent isopropyl alcohol. Other alcohols in the mixture can be either primary or secondary alcohols, which contain at least 5 carbon atoms. In some applications (eg, passenger car crankcase oil), isopropyl alcohol and other secondary
It is clear that improved results are obtained from metal phosphorodithioate derived from a mixture of secondary alcohols (e.g., 4-methyl-2-pentanol). For diesel applications, when the phosphorodithioic acid is prepared from a mixture with isopropyl alcohol and a primary alcohol (eg, isooctyl alcohol),
Improved results (ie, wear resistance) are obtained.

Considered useful in the lubricating compositions of the present invention,
Another class of phosphorodithioate additives is
Containing a mixed metal salt of (a) at least one phosphorodithioic acid of formula VII, as defined and exemplified above, and (b) at least one aliphatic or cycloaliphatic carboxylic acid. I do. The carboxylic acid can be a monocarboxylic acid or a polycarboxylic acid (these are usually
One to about three carboxy groups, preferably containing only one carboxy group). The carboxylic acid has about 2 to about 40 carbon atoms, preferably about 2 to about 40 carbon atoms.
It may contain 20 carbon atoms, conveniently from about 5 to about 20 carbon atoms. More preferred carboxylic acids have the formula R ³ COOH
(Wherein R ³ is an aliphatic or cycloaliphatic hydrocarbon-based group, preferably free of acetylenic unsaturation)
Is a carboxylic acid having the formula: Suitable acids include butanoic acid,
Included are pentanoic, hexanoic, octanoic, nonanoic, decanoic, dodecanoic, octadecanoic, and arachinic acids, as well as olefinic acids (eg, oleic, linoleic and linolenic, and linoleic acid dimers). . In most instances, R ³ is a saturated aliphatic group, particularly branched alkyl groups (e.g., isopropyl or 3-heptyl group,). Exemplary polycarboxylic acids include:
There are succinic, alkyl and alkenyl succinic acids, adipic acid, sebacic acid and citric acid.

The mixed metal salt can be prepared by simply mixing the metal salt of phosphorodithioic acid and the metal salt of carboxylic acid in the desired ratio. The equivalent ratio of phosphorodithioate to carboxylate is between about 0.5: 1 to about 400: 1. Preferably, this ratio is between about 0.5: 1 and about 200: 1. Conveniently, this ratio will be from about 0.5: 1 to about 100: 1, preferably from about 0.5: 1 to about 50: 1, more preferably about 0.5.
5: 1 to about 20: 1. In addition, this ratio ranges from about 0.5: 1 to
It may be about 4.51, preferably about 2.5: 1 to about 4.25: 1. For this purpose, the equivalent of phosphorodithioic acid is its molecular weight divided by the number of -PSSH groups therein, and the equivalent of carboxylic acid is its molecular weight divided by the number of carboxy groups therein. Value.

A second more preferred method of preparing mixed metal salts useful in this invention is to prepare a mixture of acids in the desired proportions and react the acid mixture with a suitable metal base. When this method of preparation is used, it is often possible to prepare a salt containing an excess of metal in terms of the number of equivalents of acid present; thus, containing as little as 2 equivalents of metal per equivalent of acid. Mixed metal salts can be prepared, especially mixed metal salts containing up to about 1.5 equivalents of metal. For this purpose, the equivalent of a metal is its atomic weight divided by its valency.

Variations of the above methods can also be used to prepare mixed metal salts useful in the present invention. For example, a metal salt of either acid can be mixed with another acid. The obtained mixture is further subjected to a reaction with a metal base.

Suitable metal bases for preparing the mixed metal salts include the free metals listed above and their oxides, hydroxides, alkoxides and basic salts. Examples include sodium hydroxide, potassium hydroxide, magnesium oxide, calcium hydroxide, zinc oxide, lead oxide, nickel oxide, and the like.

The temperature at which the mixed metal salt is prepared is generally between 30 ° C and about 150 ° C, preferably up to about 125 ° C. If a mixed metal salt is prepared by neutralization of a mixture of acids with a metal base, it is more preferred to use temperatures above about 50 ° C, especially above about 75 ° C. It is often advantageous to carry out the reaction in the presence of a substantially inert, normally liquid organic diluent (eg, naphtha, benzene, xylene, mineral oil, etc.). If the diluent is a mineral oil or a physically or chemically similar mineral oil, it is not necessary to remove the diluent prior to using the mixed metal salt as a lubricant or additive in a functional fluid.

U.S. Pat. Nos. 4,308,154 and 4,417,970 describe methods of preparing these mixed metal salts and disclose many examples of these mixed metal salts. Such disclosures of these patents are set forth herein.

The preparation of this mixed salt is illustrated by the following example. All parts and percentages are by weight.

Example C-23 A mixture of 67 parts (1.63 equivalents) of zinc oxide and 48 parts of mineral oil is stirred at room temperature. A mixture of 401 parts (1 equivalent) of di- (2-ethylhexyl) phosphorodithioic acid and 36 parts (0.25 equivalent) of 2-ethylhexanoic acid is added over 10 minutes. During the addition, raise the temperature to 40 ° C. When the addition is complete, the temperature is raised to 80 ° C. in 3 hours. The mixture was then vacuum removed at 100 ° C. to give 9
The desired mixed metal salt results as a 1% solution.

Example C-24 383 parts (1.2 equivalents) of dialkyl phosphorodithioic acid (containing 65% isobutyl and 35% amyl) according to the method of Example C-23, 2-ethylhexanoic acid
The product is prepared from 43 parts (0.3 equivalents), 71 parts (1.73 equivalents) zinc oxide and 47 parts mineral oil. The mixed metal salt obtained as a 90% mineral oil solution contains 11.07% zinc.

(D) Neutral and basic alkaline earth metal salts: The lubricating oil composition of the present invention also contains at least one neutral or basic alkaline earth metal salt of at least one acidic organic compound. obtain. Such salt compounds are generally designated as ash-containing detergents. The acidic organic compound can be at least one sulfur-containing acid, carboxylic acid, phosphorus-containing acid, or phenol, or a mixture thereof.

Calcium, magnesium, barium and strontium are more preferred alkaline earth metals. Salts containing a mixture of two or more ions of these alkaline earth metals can be used.

Salts useful as component (D) can be neutral or basic. The neutral salt contains a sufficient amount of alkaline earth metal to neutralize the acidic groups present in the salt anion. And this basic salt contains excess alkaline earth metal cations. Generally, the basic and overbased salts are more preferred. The term metal ratio is
The ratio of the equivalent of the metal to the equivalent of the acid group. The basic or overbased salt has a metal ratio (M
R), more particularly, having a metal ratio of about 2 to about 30 or 40.

A commonly used method for preparing basic salts (or overbased salts) is to add a mineral oil solution of the acid to a stoichiometric excess of a metal neutralizing agent (eg, a metal oxide, hydroxide). , Carbonates, bicarbonates, sulfides, etc.)
Includes heating at a temperature above 50 ° C. In addition, various accelerators can be used in the neutralization step to help mix a large excess of metal. These accelerators include compounds such as: phenolic substances (eg, phenol, naphthol); alkyls (eg, methanol, 2-propanol, octylalkyl, cellosolve carbitol); amines (eg, aniline) Phenylenediamine and dodecylamine). A particularly effective method for preparing this basic barium salt is to mix the acid with an excess of barium in the presence of a phenolic promoter and a small amount of water, and to heat the mixture to an elevated temperature ( For example, carbonation at 60 ° C. to about 200 ° C.) is included.

As mentioned above, the acidic organic compound from which the salt of component (D) is derived can be at least one sulfur-containing acid, carboxylic acid, phosphorus-containing acid, or phenol or mixtures thereof. Sulfur-containing acids include sulfonic, thiosulfonic, sulfinic, sulfenic, partially esterified sulfuric, sulfurous and thiosulfuric acids.

Sulfonic acids useful in preparing component (D) include sulfonic acids represented by the following formulas (VIII) and (IX): R _x T (SO ₃ H) _u (VIII) and R '(SO ₃ H) _r (IX) In these formulas, R' is an aliphatic or aliphatic-substituted cycloaliphatic hydrocarbon or essential hydrocarbon group, which is an acetylenic hydrocarbon group. Without unsaturation and containing up to about 60 carbon atoms). When R ′ is aliphatic,
It usually contains at least about 15 carbon atoms; when R 'is aliphatically substituted cycloaliphatic, this aliphatic substituent usually contains at least about 12 total carbon atoms. I do. Examples of R 'are alkyl, alkenyl, and alkoxyalkyl groups, wherein the aliphatic substituent is an aliphatic substituted cycloaliphatic group such that the aliphatic substituent is an alkyl, alkenyl, , Alkoxy, alkoxyalkyl, carboxyalkyl, and the like. Generally, this cycloaliphatic
It is derived from a cycloalkane or cycloalkene (eg, cyclopentane, cyclohexane, cyclohexene or cyclopentene). Particular examples of R 'include cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl, octadecenyl, and groups derived from: petroleum saturated and unsaturated paraffin waxes, and olefin polymers, including one olefin. Polymerized monoolefins containing from about 2 to 8 carbon atoms per functional monomer unit, and diolefins containing from 4 to 8 carbon atoms per monomer unit). R 'can also include other substituents such as phenyl, cycloalkyl, hydroxy, mercapto, halo,
Nitro, amino, nitrone, lower alkoxy, lower alkyl mercapto, carboxy, carboalkoxy, oxo or thio, or interrupting groups (eg, -NH-, -O-
Or -S-)) can be included as long as its essentially hydrocarbon nature is not impaired.

R in formula VIII is generally a hydrocarbon group or an essential hydrocarbon group, which is free of acetylenic unsaturation and contains from about 4 to about 60 aliphatic carbon atoms, preferably An aliphatic hydrocarbon group such as alkyl or alkenyl. However, it may also contain substituents or interrupting groups as listed above, provided that they do not impair essential hydrocarbon properties. Generally, R 'or R
Any non-carbon atoms present in them
It is not expected to exceed 10%.

T is a cyclic nucleus from which an aromatic hydrocarbon (eg, benzene, naphthalene, anthracene, or biphenyl) can be derived, or a cyclic nucleus from which a heterocyclic compound (eg, pyridine, indole or isoindole) can be derived. Usually, T is an aromatic hydrocarbon nucleus, especially a benzene nucleus or a naphthalene nucleus.

The subscript x is at least 1 and is generally 1-3. The subscripts r and y have an average value of about 1-2 per molecule and are generally also 1.

The sulfonic acid is generally petroleum sulfonic acid or synthetically prepared alkaryl sulfonic acid. Among the petroleum sulfonic acids, the most useful products are those prepared by sulfonating the appropriate petroleum fraction using continuous acid sludge removal and purification. Synthetic alkaryl sulfonic acids are usually prepared from alkylated benzenes (e.g., the Friedel-Crafts reaction product of benzene with a polymer such as tetrapropylene). The following are specific examples of sulfonic acids useful in preparing salt (D). It should be understood that such examples are also provided to illustrate salts of sulfonic acids useful as component (D). In other words, for each sulfonic acid listed, their corresponding basic alkali metal salts are also intended to be understood for purposes of illustration. (The same applies to the other acid substance tables listed below). Such sulfonic acids include mahogany sulfonic acid, bright stock sulfonic acid, petroleum sulfonic acid, mono- or polywax substituted naphthalene sulfonic acid, cetyl chlorobenzene sulfonic acid, cetyl phenol sulfonic acid, cetyl phenol disulfide sulfonic acid, cetoxy Caprylbenzenesulfonic acid, dicetylthianthrenesulfonic acid, dilauryl-β-naphtholsulfonic acid, dicaprylnitronaphthalenesulfonic acid, saturated paraffin wax sulfonic acid, unsaturated paraffin wax sulfonic acid, hydroxy-substituted paraffin wax sulfonic acid, tetraisobutylene sulfonic acid , Tetra-amylene-sulfonic acid, chloro-substituted paraffin wax sulfonic acid, nitroso-substituted paraffin wax sulfonic acid, petroleum naphthalene sulfonic acid Cetyl cyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, mono- - and poly-wax-substituted cyclohexyl sulfonic acids, dodecylbenzene sulfonic acids, "dimer alkylate" sulfonic acids, and the like are included.

Alkyl-substituted benzenesulfonic acids, where the alkyl group contains at least 8 carbon atoms,
Particularly useful, including dodecylbenzene "bottoms" sulfonic acid. The latter are acids derived from benzene. It is alkylated with a propylene tetramer or isobutene trimer to give 1, on the benzene ring,
Two, three or more branched-chain C ₁₂ substituents are introduced. Dodecylbenzene bottoms (primarily a mixture of mono- and di-dodecylbenzene) are available as a by-product from the manufacture of household cleaners. During the production of linear alkyl sulfonates (LAS), analogous products obtained from the alkylated bottoms formed are also useful in producing the sulfonates used in the present invention.

For example, by reaction with SO _3, from by-products of the manufacture of detergents, to produce a sulfonate, are known to those skilled in the art. For example, Kirk-Othmer's encyclopedia of chemical technology, 2
See the “Sulfonates” chapter of the Edition, Volume 19, pp. 291 et seq., Issued by Wiley & Sons, NY in 1969.

Other descriptions of basic sulfonic acid salts, which can be incorporated into the lubricating oil compositions of this invention as component (C), and methods for their preparation, can be found in the following US patents: US Patent 2,174,110 No. 2,202,781; 2,239,974; 2,
319,121; 2,337,552; 3,488,284; 3,595,790; and 3,798,012. These are set forth herein for their disclosure.

Suitable carboxylic acids from which useful alkaline earth metal salts (D) can be prepared include aliphatic carboxylic acids, cycloaliphatic carboxylic acids, aromatic monobasic carboxylic acids and polybasic carboxylic acids. In addition, naphthenic acid, alkyl- or alkenyl-substituted cyclopentanoic acid, alkyl- or alkenyl-substituted cyclohexanoic acid,
And alkyl- or alkenyl-substituted aromatic carboxylic acids. The aliphatic acid generally contains about 8 to about 50 carbon atoms, preferably about 12 to about 25 carbon atoms. Cycloaliphatic carboxylic acids and aliphatic carboxylic acids are more preferred. They may be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, linolenic acid, propylene tetramer substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoyl acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecyl Acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalenecarboxylic acid, stearyloctahydroindenecarboxylic acid, palmitic acid, alkyl succinic acid and alkenyl succinic acid, acid formed by oxidation of petrolatum and hydrocarbon wax, And commercial mixtures of two or more carboxylic acids, such as tall oil acids, rosin acids and the like.

The equivalent weight of an acidic organic compound is a value obtained by dividing its molecular weight by the number of acidic groups (that is, sulfonic acid groups or carboxy groups) present per molecule.

The pentavalent phosphorus-containing acid useful for preparing component (D) can be an organophosphoric acid, phosphoric acid or phosphinic acid, or a thio analog thereof.

Component (D) can also be prepared from phenol (ie, a compound containing a hydroxyl group bonded directly to an aromatic ring). The term "phenol" as used herein includes compounds having more than one hydroxyl group attached to an aromatic ring (eg, catechol, resorcinol, and hydroquinone). It also includes alkylphenols (eg, cresol and ethylphenol),
And alkenylphenols. Phenols containing at least one alkyl substituent containing about 3-100 carbon atoms (preferably about 6-50 carbon atoms), such as heptylphenol, octylphenol, dodecylphenol, tetrapropene-alkyl Phenol, octadecylphenol and polybutenylphenol) are more preferred. Phenols containing more than one alkyl substituent may also be used, but monoalkyl phenols are more preferred due to availability and ease of production.

Also useful are condensation products of the above phenols with at least one lower aldehyde or ketone. The term "lower" refers to aldehydes and ketones containing no more than 7 carbon atoms. Suitable aldehydes include formaldehyde, acetaldehyde, propionaldehyde and the like.

The equivalent weight of an acidic organic compound is a value obtained by dividing its molecular weight by the number of acid groups (ie, sulfonic acid groups or carboxy groups) present per molecule.

In certain embodiments, an overbased alkaline earth metal salt of an organic acidic compound is more preferred. At least about 2
Salts having a metal ratio or greater, generally from about 2 to about 40, more preferably up to about 20 are useful.

The amount of component (D) included in the lubricant of the present invention also
Can be varied in a wide range. Useful amounts for a particular lubricating oil composition can be readily determined by those skilled in the art. Component (D)
Functions as an auxiliary or additional cleaning agent.
The amount of the component (D) contained in the lubricant of the present invention is about 0%.
% Or from about 0.01% to about 5% or more.

The following examples illustrate the preparation of neutral and basic alkaline earth metal salts useful as component (D).

Example D-1 906 parts of an oil solution of an alkylphenylsulfonic acid (which has a number average molecular weight of 450, vapor phase osmotic pressure),
564 parts of mineral oil, 600 parts of toluene, 98.7 parts of magnesium oxide,
And 120 parts of water are blown with carbon dioxide at a temperature of 78-85 ° C. at a rate of about 3 cubic feet per hour for 7 hours. The reaction mixture is constantly stirred during carbonation. After carbonation, 165 ° C / 20
Remove volatile components to tor. and filter the residue. The filtrate is an oil solution (34%) of the desired overbased magnesium sulfonate, which has a metal ratio of about 3.
Is oil).

Example D-2 Reaction of chlorinated poly (isobutene), which has an average chlorine content of 4.3% and has, on average, 82 carbon atoms, with maleic anhydride at about 200 ° C Thus, polyisobutenyl succinic anhydride is prepared. The resulting polyisobutenyl succinic anhydride has a saponification number of 90. 1246 parts of succinic anhydride and 1000 parts of toluene
At 25 ° C., 76.6 parts of barium oxide are added to the mixture of parts. The mixture is heated to 115 ° C. and 125 parts of water are added dropwise over 1 hour. The mixture is then refluxed at 150 ° C. until all the barium oxide has reacted. Removal of volatile components and filtration gives the desired product.

Example D-3 323 parts of mineral oil, 4.8 parts of water, 0.74 part of calcium chloride, lime 79
Parts and a mixture of 128 parts of methyl alcohol,
Warm to a temperature of about 50 ° C. To this mixture is added, with mixing, 1000 parts of an alkylphenylsulfonic acid, which has an average molecular weight (vapor phase osmotic pressure) of 500.
The mixture is then blown with carbon dioxide at a temperature of about 50 ° C. at a rate of about 5.4 pounds per hour for about 2.5 hours. After carbonation, an additional amount of 102 parts of oil is added and the mixture is stripped of volatiles at a temperature of about 150-155 ° C. and a pressure of 55 mm. The residue is filtered. The filtrate is the desired oil solution of overbased calcium sulfonate, which has a calcium content of about 3.7% and a metal ratio of about 1.7.

Example D-4 A mixture of 490 parts (by weight) of mineral oil, 110 parts of water, 61 parts of heptylphenol, 340 parts of barium mahogany sulfonate, and 227 parts of barium oxide is heated at 100 ° C for 0.5 hour, and then heated at 150 ° C. Heat until The mixture is then bubbled with carbon dioxide until the mixture is substantially neutral. The mixture is filtered. This filtrate has been found to have a sulfated ash content of 25%.

(E) Carboxylic acid ester derivative composition: The lubricating oil composition of the present invention also often comprises (E-
1) at least one substituted succinic acylating agent;
-2) produced by reacting at least one alcohol or phenol of the following general formula:
(E) may contain at least one carboxylic ester derivative composition: R ³ (OH) _m (X) wherein R ³ is attached to the —OH group via a carbon bond,
Is a monovalent or polyvalent organic group, and m is an integer from 1 to about 10. This carboxylic ester derivative (E) is
In order to obtain further dispersibility, it is contained in the oil composition. In some applications, the ratio of the carboxylic acid derivative (B) to the carboxylic ester (E) present in the oil affects the properties (eg, antiwear properties) of the oil composition.

In one embodiment, the use of a carboxylic acid derivative (B) in combination with a small amount of a carboxylic acid ester (E) in the presence of a particular metal dithiophosphate (C) of the present invention (eg, 4 A 2: 1 to 2: 1 weight ratio of carboxylic acid ester) results in an oil having particularly desirable properties (eg, abrasion resistance and minimizing varnish and sludge formation). Such oil compositions are used in particular in diesel engines.

A substituted succinic acylating agent (E-1), which is reacted with an alcohol or phenol to form a carboxylic acid ester derivative, prepares the carboxylic acid derivative (B) described above, with certain exceptions. This is the same as the acylating agent (B-1) used in the reaction. The polyalkene from which the substituent is derived is characterized as having a number average molecular weight of at least about 700.

More preferred is a molecular weight (n) of about 700 to about 5000. In some more preferred embodiments, the substituents of the acylating agent have an n value of about 1300-5000, and a w /
It is derived from a polyalkene characterized by an n value. The acylating agent of this embodiment is the same as the acylating agent described above with respect to the preparation of the carboxylic acid derivative composition useful as component (B) described above. therefore,
Any of the acylating agents described above for the preparation of component (B) can be utilized in the preparation of carboxylic ester derivative compositions useful as component (E). When the acylating agent used to prepare the carboxylic ester (E) is the same as the acylating agent used to prepare the component (B), the carboxylic ester component (E) also has VI properties. Characterized as a dispersant. The combination of component (B) used in the oil of the invention with a more preferred type of component (E) also gives the oil of the invention excellent abrasion resistance properties. However, other substituted succinic acylating agents may also be used in the carboxylic ester derivative composition (this is the component (E)
Which is useful as a). For example, substituted succinic acylating agents wherein the substituent is derived from a polyalkene having a number average molecular weight of about 800 to about 1200 are useful.

Carboxylic acid ester derivative composition (E) is a composition of the above succinic acylating agent with the following hydroxy compound: this hydroxy compound is an aliphatic compound (eg, a monohydric alcohol and a polyhydric alcohol) Or it may be an aromatic compound such as phenol and naphthol. Aromatic hydroxy compounds from which esters can be derived are exemplified by the following specific examples: phenol, β-naphthol, α-naphthol, cresol, resorcinol, catechol, p, p′-dihydroxybiphenyl, 2-chlorophenol, 2,4-dibutylphenol and the like.

Alcohol (E-2) from which this ester can be derived
Contains preferably up to about 40 aliphatic carbon atoms. These alcohols can be monohydric alcohols such as: methanol, ethanol, isooctanol, dodecanol, cyclohexanol and the like. The polyhydric alcohol preferably contains 2 to about 10 hydroxy groups. These are, for example, ethylene glycol,
Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols, wherein the alkylene group has 2 to about 8 carbon atoms. Is included).

A particularly preferred class of polyhydric alcohols are those having at least three hydroxy groups. Some of them are monocarboxylic acids having about 8 to about 30 carbon atoms (eg, octanoic, oleic, stearic, linoleic, dodecanoic, or tall oil acids).
Is esterified. Examples of such partially esterified polyhydric alcohols are monooleate of sorbitol,
Sorbitol distearate, glycerol monooleate, glycerol monostearate, erythritol di-dodecanoate.

This ester (E) can be prepared by one of various known methods. For convenience and because of the superior properties of the resulting ester, a more preferred method involves the reaction of a suitable alcohol or phenol with succinic anhydride substantially substituted with a hydrocarbon. This esterification is usually carried out at a temperature above about 100 ° C, preferably at 150 ° C.
And at a temperature between 300 and 300 ° C. Water formed as a by-product is removed by distillation as the esterification proceeds.

The relative proportions of succinic and hydroxy reactants that can be used depends to a large extent on the type of product desired and on the number of hydroxyl groups present in the molecule of the hydroxy reactant. . For example, to form a succinic half ester (ie, one in which only one of the two acid groups is esterified), one mole of the monohydric alcohol is added to each mole of the substituted succinic reactant. Use is included. In contrast, the formation of the diester of succinic acid is based on two moles of alcohol for each mole of acid.
The use of moles is included. On the other hand, one mole of the hexahydric alcohol can be combined with about six moles of succinic acid to form an ester. In this ester, each of the 6
Hydroxyl groups can be esterified by one of the two acid groups of succinic acid. Therefore, the maximum percentage of succinic acid that can be used with the polyhydric alcohol is determined by the number of hydroxyl groups present in the molecule of the hydroxy reactant. In certain embodiments, esters obtained by reacting equimolar amounts of the succinic and hydroxy reactants are preferred.

Methods for preparing this carboxylic acid ester (E) are known in the art and need not be further elaborated herein. See, for example, U.S. Pat. No. 3,522,179. The content of this patent is set forth herein with respect to its disclosure of the preparation of carboxylic ester compositions useful as component (E). An acylating agent wherein the substituents have an n of at least about 1300 to about 5000, and a w of 1.5 to about 4
(derived from a polyalkene characterized by a / n ratio) is described in US Pat. No. 4,234,435.
The contents of this patent are set forth above. As noted above, the acylating agents described in the '435 patent also
For each equivalent of substituent, it is characterized as having, on average, at least 1.3 succinic groups in its structure.

The following examples illustrate the esters (E) and methods for preparing such esters.

Example E-1 Polyisobutene, which has a molecular weight of 1000
Was chlorinated to a chlorine content of 4.5%, then the chlorinated polyisobutene was substantially displaced by hydrocarbons by heating with 1.2 mole proportions of maleic anhydride at a temperature of 150-220 ° C. Succinic anhydride is prepared. The resulting succinic anhydride therefore has an acid number of 130. A mixture of 874 g (1 mol) of succinic anhydride and 104 g (1 mol) of neopentyl glycol was heated at 240-250 ° C. /
Hold at 30mm for 12 hours. This residue is a mixture of esters obtained by esterifying one or two hydroxy groups of the glycol. It is 10
It has a saponification number of 1 and an alcoholic hydroxy content of 0.2%.

Example E-2 A mixture of 2185 g of the anhydride of Example E-1, 480 g of methanol and 1000 cc of toluene was heated at 50-65 ° C. for 3 hours while bubbling hydrogen chloride through the reaction mixture. The substantially hydrocarbon substituted succinic anhydride dimethyl ester of Example D-1 is prepared. Then
The mixture is heated at 60-65 ° C. for 2 hours, dissolved in benzene, washed with water, dried and filtered. The filtrate is heated at 150 ° C./60 mm to remove volatile components. This residue is the desired dimethyl ester.

The carboxylate derivatives described above and obtained by reacting an acylating agent with a hydroxy-containing compound (e.g., an alcohol or a phenol) may further comprise an amine (E-3) (especially a polyamine) in the following manner. This method is as described above for the reaction of the acylating agent (B-1) with the amine (B-2) in preparing the component (B). In some embodiments, the amount of amine provided for reaction with the ester is such that there is at least about 0.01 equivalents of amine for each equivalent of acylating agent initially used in the reaction with the alcohol. If the acylating agent is reacted with the alcohol in such an amount that at least one equivalent of the alcohol is present for each equivalent of the acylating agent, the minor amount of amine may be present in the non-esterified Sufficient to provide a reaction with a small amount of carboxyl groups. In some more preferred embodiments, the amine-modified carboxylic acid ester utilized as component (E) comprises from about 1.0 to 2.0 per equivalent of the acylating agent.
It is prepared by reacting an equivalent (preferably about 1.0 to 1.8 equivalents) of a hydroxy compound with up to about 0.3 equivalents (preferably about 0.02 to about 0.25 equivalents) of a polyamine.

In another embodiment, the carboxylic acylating agent can be simultaneously reacted with both an alcohol and an amine. Generally, there will be at least about 0.01 equivalent of alcohol, and at least 0.01 equivalent of amine. However, the total equivalents of this conjugate should be at least about 0.5 equivalents per equivalent of acylating agent. These carboxylic ester derivative compositions useful as component (E) include:
It is known in the art. Many methods of preparing these derivatives are described, for example, in U.S. Pat.Nos. 3,957,854 and 4,234,435.
No. The contents of these patents are set forth above. The following specific examples illustrate the preparation of this ester. Here, both the alcohol and the amine are subjected to the reaction with the acylating agent.

Example E-3 334 parts (0.52 equivalent) of the polyisobutene-substituted succinic acylating agent prepared in Example E-2, 548 parts of mineral oil, 30 parts of pentaerythritol (0.88 equivalent), polyglycol (Po
8.6 parts (0.0057 equivalents) of lyglycol) 112-2 demulsifier (obtained from Dow Chemical Company) are heated at 150 ° C. for 2.5 hours. The reaction mixture is heated to 210 ° C. for 5 hours and maintained at 210 ° C. for 3.2 hours. The reaction mixture is
Cool to <RTIgt; C </ RTI> and add 8.5 parts (0.2 equivalents) of a commercial mixture of ethylene polyamines, which have an average of about 3 to about 10 nitrogen atoms per molecule. The reaction mixture is heated at 205 ° C. for 3 hours while blowing with nitrogen to remove volatile components from the reaction mixture and then filtered to give a filtrate as an oil solution of the desired product.

Example E-4 A mixture of 322 parts (0.5 equivalents) of the polyisobutene-substituted succinic acylating agent prepared in Example E-2, 68 parts (2.0 equivalents) of pentaerythritol, and 508 parts of mineral oil was mixed with 204-
Heat at 227 ° C. for 5 hours. The reaction mixture is heated at 162 ° C.
Cool and add 5.3 parts (0.13 equivalents) of a commercially available ethylene polyamine mixture, which has an average of about 3 to 10 nitrogen atoms per molecule. The reaction mixture is heated at 162-163 ° C. for 1 hour, then cooled to 130 ° C. and filtered. This filtrate is an oil solution of the desired product.

Example E-5 Polyisobutene 1000 having a number average molecular weight of about 1000
And a mixture of 108 parts of maleic anhydride (1.1 mol) are heated to about 190 ° C. and 100 parts of chlorine (1.43 mol)
Is added from below the surface for about 4 hours. During this time, the temperature is maintained at about 185-190 ° C. Then, to this mixture:
At this temperature, nitrogen is blown for several hours. This residue is the desired polyisobutene-substituted succinic acylating agent.

A solution of the above prepared acylating agent (1000 parts) in mineral oil (857 parts) was heated to about 150 ° C. while stirring, and while stirring,
Add 109 parts (3.2 equivalents) of pentaerythritol. Nitrogen was blown into this mixture and allowed to heat
Upon heating, an oil solution of the desired carboxylic ester intermediate is formed. This intermediate is treated with ethylene polyamine (which averages about 3 to about
19.25 parts (0.46) of a commercial mixture of 10 nitrogen atoms)
Equivalent). The reaction mixture is heated at 205 ° C. for 3 hours while blowing with nitrogen to remove volatile components and filtered. The filtrate is an oil solution (45% oil) of the desired amine-modified carboxylic acid ester, which contains 0.35% nitrogen.

Example E-6 polyisobudene (which has a number average molecular weight of 2020 and a
A mixture of 1000 parts (0.495 mol) having a weight average molecular weight of 6049) and 115 parts (1.17 mol) of maleic anhydride is heated to 184 ° C. over 6 hours. During this time, 85 parts (1.2 mol) of chlorine are added below the surface. An additional 59 parts (0.83 mol) of chlorine are added at 184-189 ° C. over 4 hours. The mixture is blown with nitrogen at 186-190 ° C. for 26 hours. This residue is a polyisobutene-substituted succinic anhydride having a total acid number of 95.3.

A solution of 409 parts (0.66 mol) of this substituted succinic anhydride in 191 parts of mineral oil was heated to 150 ° C., and pentaerythritol 42.5 parts
Parts (1.19 equivalents) at 145-150 ° C. while stirring.
Add over minutes. Nitrogen is blown into this mixture,
Heating to 205-210 ° C. for about 14 minutes results in an oil solution of the desired polyester intermediate.

To 988 parts of this polyester intermediate, which contains 0.69 equivalents of the substituted succinic acylating agent and 1.24 equivalents of pentaerythritol, is added 4.7 parts of diethylenetriamine.
Add 4 parts (0.138 eq) at 160 ° C. over 1/2 hour. Stirring is continued at 160 ° C. for 1 hour, after which 289 parts of mineral oil are added. The mixture is heated at 135 ° C. for 16 hours and filtered at the same temperature using a filter aid. The filtrate is a 35% mineral oil solution of the desired amine-modified polyester. It has a nitrogen content of 0.16% and a residual acid number of 2.0.

Example E-7 (a) Polyisobudene 10 having a number average molecular weight of about 1000
A mixture of 00 parts and 108 parts of maleic anhydride (1.1 mol) is heated to about 190 ° C. and 100 parts of chlorine (1.43 mol)
Is added from below the surface for about 4 hours. During this time, the temperature is maintained at about 185-190 ° C. Then, to this mixture:
At this temperature, nitrogen is blown for several hours. This residue is the desired polyisobutene-substituted succinic acylating agent.

(B) A solution of the acylating agent preparation (a) 1000 parts in 857 parts mineral oil is heated to about 150 ° C. with stirring and 109 parts (3.2 equivalents) of pentaerythritol are added with stirring.
The mixture is blown with nitrogen for about 14 hours and
Upon heating to 0 ° C., an oil solution of the desired carboxylic ester intermediate is formed. To this intermediate is added 19.25 parts (0.46 equivalents) of a commercial mixture of ethylene polyamine, which has an average of about 3 to about 10 nitrogen atoms per molecule. The reaction mixture is heated at 205 ° C. for 3 hours while blowing with nitrogen to remove volatile components and filtered. The filtrate is an oil solution (45% oil) of the desired amine-modified carboxylic acid ester, which contains 0.35% nitrogen.

Example E-8 (a) 1000 parts (0.495) of polyisobudene, which has a number average molecular weight of 2020 and a weight average molecular weight of 6049
Mol), and a mixture of 115 parts of maleic anhydride (1.17 mol) is heated to 184 ° C. over 6 hours. During this time, 85 parts (1.2 mol) of chlorine are added below the surface. An additional 59 parts (0.83 mol) of chlorine are added at 184-189 ° C. over 4 hours. At 186-190 ° C, 26
Blow nitrogen for hours. This residue is a polyisobutene-substituted succinic anhydride having a total acid number of 95.3.

(B) 409 parts (0.66 mol) of this substituted succinic anhydride in mineral oil 1
Heat 91 parts of the solution to 150 ° C, and add pentaerythritol 4
2.5 parts (1.19 equivalents) at 145-150 ° C. with stirring
Add over 10 minutes. The mixture is blown with nitrogen and heated to 205-210 ° C. for about 14 hours to produce an oil solution of the desired polyester intermediate.

To 988 parts of this polyester intermediate, which contains 0.69 equivalents of the substituted succinic acylating agent and 1.24 equivalents of pentaerythritol, is added 4.7 parts of diethylenetriamine.
Add 4 parts (0.138 eq) at 160 ° C. over 1/2 hour. Stirring is continued at 160 ° C. for 1 hour, after which 289 parts of mineral oil are added. The mixture is heated at 135 ° C. for 16 hours and filtered at the same temperature using a filter aid. The filtrate is a 35% mineral oil solution of the desired amine-modified polyester. It has a nitrogen content of 0.16% and a residual acid number of 2.0.

(F) Chlorinated alkali metal salt: The lubricating oil composition of the present invention may also contain at least one basic alkali metal salt of a sulfonic acid or carboxylic acid. This component is in the art-recognized metal-containing composition. These compositions are:
They are individually indicated by names such as "basic", "super based" and "over based" salts or complexes. Their method of preparation is usually "overbased"
As shown. The term “metal ratio” is often
It is used to define the amount of metal in these salts or complexes relative to the amount of organic anions. This metal ratio is
It is defined as the ratio of the number of equivalents of metal actually present to the number of equivalents of metal present in the normal salt, based on the usual stoichiometry of the compound involved.

A general description of certain alkali metal salts useful as component (F) can be found in US Pat. No. 4,326,972 (Chamberlin)
It is included in. The contents of this patent are set forth herein for disclosure of useful alkali metal salts and methods for preparing the salts.

Alkali metals present in the basic alkali metal salts mainly include lithium, sodium and potassium, with sodium and potassium being more preferred.

The sulfonic and carboxylic acids useful in preparing component (F) include those previously described as useful in preparing neutral and basic alkaline earth metal salts (D). Is done.

The equivalent weight of an acidic organic compound is a value obtained by dividing its molecular weight by the number of acidic groups (that is, sulfonic acid groups or carboxy groups) present per molecule.

In some more preferred embodiments, the alkali metal salt (F) has a metal ratio of at least about 2, more generally a metal ratio of about 4 to about 40, preferably a metal ratio of about 6 to about 30, and especially about 8 Basic alkali metal salts having a metal ratio of from about to about 25.

In another more preferred embodiment, the basic sulfonate (F) is an oil-soluble dispersion. This dispersion comprises the following (F-1) and (F-2) at a temperature between the solidification temperature of the reaction mixture and its decomposition temperature for a period sufficient to form a stable dispersion. Prepared by contacting: (F-1) at least one acidic gaseous substance selected from the group consisting of: carbon dioxide, hydrogen sulfide, and sulfur dioxide; (F-2-a) at least one oil-soluble sulfonic acid, or a derivative thereof, which can undergo overbasing; (F-2-b) at least one alkali metal compound or basic alkali metal (F-2-c) at least one lower aliphatic alcohol, alkylphenol, or sulfurized alkylphenol; and (F-2-d) at least one oil-soluble carboxy;
Or their functional derivatives.

When (F-2-c) is an alkylphenol or a sulfurized alkylphenol, the component (F-2-d) is optional. Suitable basic sulfonates can be obtained from the mixture (F-2)
Can be prepared with or without a carboxylic acid.

Reagent (F-1) is at least one acidic gaseous substance. This substance can be carbon dioxide, hydrogen sulfide or sulfur dioxide; mixtures of these gases are also
Useful. Carbon dioxide is more preferred.

As mentioned above, component (F-2) is generally a mixture containing at least four components. Here, component (F-2-a) is at least one oil-soluble sulfonic acid as defined above, or a derivative thereof that can undergo overbasing. Mixtures of sulfonic acids and / or their derivatives can also be used. Sulfonic acid derivatives that can be overbased include their metal salts, especially alkaline earth metal salts (eg, zinc salts and lead salts); ammonium salts and amine salts (eg, ethylamine salts, butylamine salts and ethylene polyamine salts) ); And esters such as ethyl, butyl and glycerol esters.

Component (F-2-b) is preferably and generally at least one basic alkali metal compound. Examples of basic alkali metal compounds include hydroxide,
There are alkoxides (typically where the alkoxy group contains up to 10 carbon atoms, preferably up to 7 carbon atoms), hydrides and amides. Therefore, useful basic alkali metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium propoxide, lithium methoxide, potassium ethoxide, sodium butoxide, lithium hydride, sodium hydride, hydride Potassium, lithium amide, sodium amide and potassium amide are included. Sodium hydroxide and sodium lower alkoxides (ie, alkoxides containing up to 7 carbon atoms)
Particularly preferred. For the present invention, the component (F-2-b)
Is equivalent to its molecular weight, since this alkali metal is monovalent.

Component (F-2-c) can be at least one lower aliphatic alcohol, preferably a monohydric or polyhydric alcohol. Exemplary alcohols include methanol, ethanol, 1-propanol, 1-hexanol, isopropanol, isobutanol, 2-pentanol, 2,2-dimethyl-1-propanol, ethylene glycol, 1-3-propanediol and 1,3-propanol. There is 5-pentadiol. The alcohol can also be a glycol ether such as Methyl Cellosolve. Among these, more preferred alcohols are methanol, ethanol and propanol, and methanol is particularly preferred.

Component (F-2-c) can also be at least one alkyl phenol or sulfurized alkyl phenol. Sulfurized alkylphenols are, in particular, (F-2-b)
Is more preferably a potassium compound or one of its basic compounds (eg, potassium hydroxide). As used herein, the term "phenol" includes compounds having one or more hydroxyl groups attached to an aromatic ring. The aromatic ring can be a benzyl or naphthyl ring. The term "alkylphenol" includes mono- and di-alkylphenols. Here, each alkyl substituent contains from about 6 to about 100 carbon atoms, preferably from 6 to about 50 carbon atoms.

Exemplary alkyl phenols include heptyl phenol, octyl phenol, decyl phenol, dodecyl phenol, polypropylene (n is about 150) substituted phenols, polyisobutene (n is about 1200) substituted phenols, cyclohexyl phenol.

Also useful are the condensation products of the above phenols with at least one lower aldehyde or ketone. The term "lower" refers to aldehydes or Kents containing no more than 7 carbon atoms. Suitable aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and benzaldehyde. Reagents that produce aldehydes are also suitable. This reagent includes, for example, paraformaldehyde, trioxane, methylol, methylformcel and paraaldehyde.
Formaldehyde and reagents that produce formaldehyde are particularly preferred.

Sulfurized alkyl phenols include phenol sulfides, disulfides or polysulfides.
The sulfurized phenol can be derived from any suitable alkyl phenol by methods known to those skilled in the art. Many sulfurized phenols are commercially available. The sulfurized alkyl phenol can be prepared by reacting an alkyl phenol with elemental sulfur and / or sulfur monohalide (eg, sulfur monochloride). This reaction can be carried out in the presence of an excess of base, resulting in salts of sulfides, disulfides or mixtures of polysulfides, which may be formed depending on the reaction conditions. The substance used in preparing component (F-2) in the present invention is a product obtained by this reaction. U.S. Patent 2,971,940 and
No. 4,309,293 discloses various sulfurized phenols. These phenols are examples of the component (F-2-c). The disclosures of these patents are set forth herein.

The equivalent of the component (F-2-c) is a value obtained by dividing the molecular weight by the number of hydroxyl groups per molecule.

Component (F-2-d) is at least one oil-soluble carboxylic acid, as defined above, or a functional derivative thereof. Particularly suitable carboxylic acids are those of the formula R ⁵ (COOH) _n . Wherein n is an integer from 1 to 6, preferably 1 or 2, and R ⁵ is a saturated or substantially saturated aliphatic group having at least 8 aliphatic carbon atoms (preferably Hydrogen group). Depending on the value of n, R ⁵ is a monovalent 5 monovalent group.

R ⁵ may contain a non-hydrocarbon substituent. However, these substituents do not substantially change their hydrocarbon properties. Such substituents are preferably present in an amount not exceeding about 20% by weight. Exemplary substituents include component (F-2)
With reference to -a), the non-hydrocarbon substituents mentioned above are included. R ⁵ also may contain olefinic unsaturation up to at most about 5%, preferably 2% olefinic bond that does not exceed (which carbon exists - based on the total number of carbon covalent bond) containing I can do it. The total number of carbon atoms in R ⁵ is
Normally, depending on the raw material for R ^5, are approximately 8-700. As described below, a more preferred group of carboxylic acids and derivatives thereof comprises an olefinic polymer or a halogenated olefinic polymer and an α, β-unsaturated acid or anhydride (eg, acrylic acid, methacrylic acid). Acid, maleic acid or fumaric acid, or maleic anhydride)
To form the corresponding substituted acids or their derivatives,
It is prepared by reacting. In these products
R ⁵ groups, the number average molecular weight of from about 150 to about 10,000, usually,
It has a number average molecular weight of about 700 to about 5000 (as determined, for example, by gel permeation chromatography).

Monocarboxylic acids useful as component (F-2-d) include:
It has the formula R ⁵ COOH. Examples of such acids are caprylic acid,
There are capric, palmitic, stearic, isostearic, linoleic and behenic acids. A particularly preferred group of monocarboxylic acids is prepared by reacting a halogenated olefin polymer (eg, chlorinated polybutene) with acrylic acid or methacrylic acid. Suitable dicarboxylic acids include substituted succinic acids having the formula Is included: Here, R ⁶ is the same as R ⁵ defined above.

R ⁶ can be a group derived from an olefin polymer. This group, by the polymer of the following monomer,
Formed: ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-pentene, 1-hexene and 3-hexene. R ⁶ may also be derived from a high molecular weight, substantially unsaturated petroleum fraction. The hydrocarbon-substituted succinic acids and their derivatives constitute the most preferred class of carboxylic acids for use as component (F-2-d).

Carboxylic acids of the class described above, and their derivatives, derived from olefinic polymers are known in the art. Representative examples of the types useful in the present invention, as well as their methods of preparation, are described in many US patents.

Functional derivatives of the aforementioned acids useful as component (F-2-d) include anhydrides, esters, amides, imides, amidines and metal salts, or ammonium salts. Succinic acid substituted with an olefinic polymer and a monoamine or polyamine (especially a polyalkylene polyamine; which has up to about 10 amino nitrogens)
Particularly suitable. These reaction products generally contain a mixture of one or more amides, imides and amidines. Reaction products of polyethyleneamines, which contain up to about 10 nitrogen atoms, and polybutene-substituted succinic anhydrides, where the polybutene groups mainly contain isobutene units, are particularly useful. It is. Functional derivatives of this group are prepared by post-treating amine-anhydride reaction products with carbon disulfide, boron compounds, nitriles, ureas, thioureas, guanidines, alkylene oxides or the like. Compositions. Such substituted succinic acid semi-amides, semi-metal salts and semi-esters, semi-metal salt derivatives are also useful.

Esters prepared by the reaction of a substituted acid or anhydride with a monohydric or polyhydric hydroxy compound (eg, an aliphatic alcohol or phenol) are also useful. More preferred are esters of olefinic polymer-substituted succinic acids or anhydrides with polyhydric aliphatic alcohols, which contain 2-10 hydroxyl groups and up to about 40 aliphatic carbon atoms. . This class of alcohols includes ethylene glycol, glycerol, sorbitol, pentaerythritol, polyethylene glycol, diethanolamine, triethanolamine, N, N'-di (hydroxyethyl) ethylenediamine, and the like. When the alcohol contains a reactive amino group, the reaction product may contain the product obtained by reaction of an acid group with both a hydroxyl group and an amino function. Thus, the reaction mixture may contain half esters, half amides, esters, amides, and imides.

The equivalent ratio of the components of the reagent (F-2) can be widely varied. In general, the component (F-a) relative to the component (F-2-a)
The ratio of 2-b) is at least about 4: 1, usually about 4: 1.
It does not exceed 0: 1, preferably between 6: 1 and 30: 1, most preferably between 8: 1 and 25: 1. This ratio is sometimes 40:
Such excesses, although allowed to exceed one, are usually
Not fit for a useful purpose.

The equivalent ratio of component (F-2-c) to component (F-2-a) is between about 1:20 and 80: 1, preferably between about 2: 1 and 50: 1. As mentioned above, when the component (F-2-c) is an alkylphenol or a sulfurized alkylphenol, the intervention of the carboxylic acid (F-2-d) is optional. When component (F-2-d) is present in the mixture, the equivalent ratio of component (F-2-d) to component (F-2-a) generally ranges from about 1: 1 to about 1:20. , Preferably from about 1: 2 to about 1:10
It is.

Up to approximately the stoichiometric amount of acidic substances, this (F-1)
Is subjected to a reaction with (F-2). In some embodiments,
This acidic substance is added to the (F-2) mixture at a constant rate. This reaction proceeds rapidly. The addition ratio of (F-1) is not important. However, if the temperature of the mixture rises too quickly due to the exothermic nature of the reaction, this addition rate must be reduced.

If (F-2-c) is an alcohol, the reaction temperature is not critical. Generally, this temperature is between the solidification temperature of the reaction mixture and its decomposition temperature (ie, the lowest decomposition temperature of all of its components). Typically, this temperature is from about 25C to about 200C, preferably from about 50C to about 150C. Reagents (F-1) and (F-2) are conveniently
Contact is made at the reflux temperature of the mixture. This temperature obviously depends on the boiling points of the various components. ;therefore,
When methanol is used as component (F-2-c), this contact temperature is at or below the reflux temperature of methanol.

When reagent (F-2-c) is an alkylphenol or a sulfurized alkylphenol, the reaction temperature must be at or above the azeotropic temperature of the water-diluent so that the water formed during the reaction can be removed. .

This reaction is usually performed under atmospheric pressure. But,
Pressures above atmospheric pressure often promote the reaction and the reagent (F
Promote optimal use of -1). This step can also be performed under reduced pressure. However, it is rarely done under reduced pressure for obvious practical reasons.

The reaction is usually carried out in the presence of a substantially inert, normally liquid, organic diluent, which functions as both a dispersant and a reaction medium; a low viscosity lubricating oil. The diluent is at least about 1% of the total weight of the reaction mixture.
It is contained at 10%.

As soon as the reaction is completed, all solids in the mixture are removed, preferably by filtration or other conventional methods. Generally, easily removable diluents, alcoholic promoters, and water formed during the reaction can be removed by conventional methods (eg, distillation). It is usually desirable to remove substantially all of the water from the reaction mixture. The presence of water makes filtration difficult and results in the formation of undesirable emulsions in fuels and lubricants. All of the water present is easily removed by heating at atmospheric or reduced pressure or by azeotropic distillation. In one embodiment, when basic potassium sulfonate is desired as component (F), the potassium salt is prepared using carbon dioxide and a sulfurized alkylphenol as component (F-2-c). The use of a sulfurized phenol results in a high metal ratio basic salt, forming a more uniform and stable salt.

The basic salt or complex of component (F) can be a solution or, more suitably, a stable dispersion. Alternatively, they may be considered as "polymer salts" formed by the reaction of acidic substances, oil-soluble salts to be overbased, and metal compounds. In view of the above, these compositions are most conveniently defined in relation to the manner in which the composition can be formed.

Using alcohols as component (F-2-c) to prepare alkali metal salts of sulfonic acids, which have a metal ratio of at least about 2, preferably between about 4 and 40 The above method is described in Canadian Patent No. 1,055,700.
No. (this corresponds to UK Patent No. 1,481,553)
In more detail. The contents of these patents are set forth herein with respect to the disclosure of such a method. The preparation of an oil-soluble dispersion of an alkali metal sulfonate useful as component (F) in the lubricating oil composition of this invention is illustrated in the following examples.

Example F-1 790 parts (1 equivalent) of alkylated benzenesulfonic acid and 71 parts (about 560 equivalents) of polybutenyl succinic anhydride, which mainly contains isobutene units, 176 parts of mineral oil 176.
To parts of the solution are added 320 parts (8 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. The temperature of the mixture increases to 89 ° C. (reflux) in 10 minutes due to exotherm. During this time, the mixture is blown with carbon dioxide at 4 cfh. (Cubic feet / hr). Temperature gradually 74
Continue carbonation for about 30 minutes while lowering to ° C. The methanol and other volatiles are removed from the carbonated mixture by blowing nitrogen at 2 cfh.
During this time, the temperature is raised slowly to 150 ° C. over 90 minutes. After the removal is complete, the remaining mixture is maintained at 155-165 ° C. for about 30 minutes and, upon filtration, the desired basic sodium sulfonate, which has a metal ratio of about 7.75
Oil solution is formed. This solution contains 12.4% oil.

Example F-2 A solution of 780 parts (1 equivalent) of alkylated benzenesulfonic acid and 119 parts of polybutenyl succinic anhydride in 442 parts of mineral oil was prepared according to the method of Example F-1 using sodium hydroxide.
Mix with 800 parts (20 equivalents) and 704 parts of methanol (22 equivalents). The mixture is blown with carbon dioxide at 7 cfh. For 11 minutes while slowly raising the temperature to 97 ° C.
Reduce the carbon dioxide blowing rate to 6 cfh.
The temperature is slowly reduced to 88 ° C over about 40 minutes. The carbon dioxide blowing rate is 5 cfh in about 35 minutes.
To lower. The temperature is slowly reduced to 73 ° C.
Volatile components are removed by bubbling nitrogen through the carbonated material at 2 cfh. For 105 minutes while slowly raising the temperature to 160 ° C. After removal is complete, the mixture is maintained at 160 ° C. for an additional 45 minutes and then filtered to give the desired basic sodium sodium sulfonate, which comprises about
(Having a metal ratio of 19.75). This solution contains 18.7% oil.

The lubricating oil composition of the present invention may also contain a friction modifier to provide the lubricating oil with additional desirable friction characteristics. Generally, from about 0.01% to about 2 or 3% by weight of the friction modifier is sufficient to provide improved performance. Various amines, especially tertiary amines, are effective friction modifiers. Examples of tertiary amine friction modifiers include N-
Fatty alkyl-N, N-diethanolamine, N-fatty alkyl-N, N-diethoxyethanolamine and the like are included. Such tertiary amines can be prepared by reacting a fatty alkylamine with a suitable number of moles of ethylene oxide. Tertiary amines derived from naturally occurring materials such as coconut oil and oleoamine are commercially available under the trade name "Ethomeen". Specific examples include the Ethomeen-C series and the Ethomeen-O series.

Partial fatty acid esters of polyhydric alcohols are useful as friction modifiers. This fatty acid generally comprises from about 8 to about
The ester containing 22 carbon atoms and is obtained by reaction with a dihydric or polyhydric alcohol containing 2 to about 8 or 10 carbon atoms. Suitable fatty acid esters include sorbitan monooleate,
Includes sorbitan dioleate, glycerol monooleate, glycerol dioleate and mixtures thereof. This includes commercial mixtures such as Emerest 2421 (Emily Industries). Other examples of partial fatty acid esters of polyhydric alcohols are described in KSMarkley, Ed.
"Fatty Acids", Volume 2, Part I and Part V, can be found in Interscience Publishing (1968).

Sulfur-containing compounds (eg, sulfurized C _12-24 fats,
Alkyl sulfides and polysulfides, wherein the alkyl group contains 1 to 8 carbon atoms),
And the sulfided polyolefin may also function as a friction modifier in the lubricating oil composition of the present invention.

(G) Neutral and basic salts of phenol sulfide: In certain embodiments, the oils of the invention may contain at least one neutral or basic alkaline earth metal salt of an alkyl phenol sulfide. This oil is
The phenol sulfide may contain from about 0% to about 2% or 3%. In most cases, the oil may contain from about 0.01% to about 2% by weight of the basic salt of phenol sulfide. The term "basic" is used herein in the same manner as that used in the definitions of the other components above. That is, the term refers to a salt having a metal ratio greater than 1 when it is mixed with the oil composition of the present invention. The neutral and basic salts of the phenol sulfide impart oxidation resistance and cleaning properties to the oil composition, and the Caterpillar test (Caterpilla test)
Improve oil performance in rtesting).

The alkyl phenol from which the sulfide salt is prepared generally comprises a phenol containing a hydrocarbon substituent having at least about 6 carbon atoms; the substituent containing up to about 7000 aliphatic carbon atoms. I can do it.
Substantial hydrocarbon substituents as defined above also
Included. More preferred hydrocarbon substituents are derived from polymers of olefins such as ethylene, propene and the like.

The term "alkylphenol sulfide" refers to di- (alkylphenol) monosulfide, disulfide, polysulfide, and other products, which are obtained by reacting the alkylphenol with sulfur monochloride, sulfur dichloride or elemental sulfur. Has a meaning that includes The molar ratio of phenol to sulfur compound is about
It can be from 1: 0.5 to about 1: 1.5 or more. For example, phenol sulfide can be easily obtained by mixing 1 mol of alkylphenol and 0.5-1.5 mol of sulfur dichloride at a temperature of about 60 ° C. or higher. The reaction mixture is typically maintained at about 100 ° C. for about 2-5 hours.
Thereafter, the obtained sulfide is dried and filtered. When using elemental sulfur, temperatures of about 200 ° C. or higher are sometimes desirable. It is also desirable to carry out this drying operation in the presence of nitrogen or a similar inert gas.

Suitable basic alkyl phenol sulfides are described, for example, in U.S. Patent Nos. 3,372,116, 3,410,798 and 3,562,15.
No. 9 and their contents are shown here.

The following examples illustrate the preparation of these basic materials.

Example G-1 Sulfur monochloride and polyisobutenylphenol (where the polyisobutenyl substituent has an average of 23.8 carbon atoms) are treated with sodium acetate, which reduces the color of the product. Phenol sulfide is prepared by reacting in the presence of an acid acceptor used to prevent phenol sulfide. 1755 parts of this phenol sulfide, mineral oil
A mixture of 500 parts, 335 parts of calcium hydroxide and 407 parts of methanol was heated to about 43-50 ° C.
Bubble carbon dioxide for 7.5 hours. The mixture is then heated to drive off volatiles and an additional 422.5 parts of oil are added to give a 60% oil solution. This solution contains 5.6% calcium and 1.59% sulfur.

(H) Sulfurized olefins: The oil compositions of the present invention also include (H) one or more sulfur-containing compounds useful in improving the antiwear, extreme pressure and oxidation resistance properties of lubricating oil compositions. A composition may be included. The olefin is an aliphatic, arylaliphatic or cycloaliphatic olefinic hydrocarbon, which comprises from about 3 to
Containing about 30 carbon atoms).

The olefinic hydrocarbon contains at least one olefinic double bond. This double bond is defined as a non-aromatic bond; that is, it is connected to two aliphatic carbon atoms. Propylene, isibbutene and their dimers, trimers and tetramers, and mixtures thereof are particularly more preferred olefinic compounds. Of these compounds, isobutene and diisobutene are particularly desirable because of their availability and from which compositions with particularly high sulfur contents can be prepared.

The contents of U.S. Pat. Nos. 4,119,549 and 4,505,830 are set forth herein for their disclosure of suitable sulfurized olefins useful in the lubricating oils of the present invention. Some specific sulfurized compositions are described in their working examples.

At least one cycloaliphatic radical, which has at least two nuclear carbon atoms in one cycloaliphatic radical, or two nuclear carbon atoms in different cycloaliphatic radicals through a divalent sulfur bond ) Are useful in component (H) in the lubricating oil compositions of the present invention. These types of sulfur compounds are described, for example, in Reissue Patent Re 27,331.
And their disclosures are set forth herein.
This sulfur bond contains at least two sulfur atoms. Sulfurized Diels-Under adducts are examples of such compositions.

The following examples are illustrative of the preparation of such compositions.

Example H-1 (a) A mixture containing 400 g of toluene and 66.7 g of aluminum chloride is charged to a 2 liter flask equipped with a stirrer, a nitrogen introducing tube, and a reflux condenser cooled with solid carbon dioxide. 640 g of butyl acrylate (5
The second mixture containing mol) and toluene 240.8G, while maintaining the temperature in the range of 37-58 ℃, added to AlCl ₃ for 0.25 hours. Thereafter, 313 g (5.8 mol) of butadiene are added to the slurry over a period of 2.75 hours while maintaining the temperature of the reaction mass at 60-61 ° C. by external cooling. The reaction mass is blown with nitrogen for about 0.33 hours, then transferred to a 4 liter separatory funnel and concentrated hydrochloric acid
Wash with 0 g of water 1100 g solution. The product is then
Two additional water washes with 1000 ml of water for each wash. Subsequently, the washed reactants are distilled to remove unreacted butyl acrylate and toluene. The residue of this first distillation stage is further distilled at a pressure of 9-10 millimeters of mercury. As a result, at a temperature of 105-115 ° C,
785 g of the desired adduct are collected.

(B) The butadiene-butyl acrylate adduct (4550 g, 25 mol) and 1600 g (50 mol) of sulfur as prepared above were placed in a 12 liter flask equipped with a stirrer, reflux condenser and nitrogen inlet tube. Filling). The reaction mixture is heated at a temperature in the range of 150-155 ° C for 7 hours. During this time, nitrogen is passed through the mixture at a rate of about 0.5 cubic feet per hour. After heating, the mass is cooled to room temperature and filtered. The filtrate is the sulfur-containing product.

Other extreme pressure agents and corrosion inhibitors and antioxidants may also be included. These reagents include chlorinated aliphatic hydrocarbons (eg, chlorinated waxes); organic sulfides and polysulfides (eg, benzyl disulfide, bis (chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfide methyl ester of oleic acid) Sulfided alkylphenols, dipentene sulfides, and terpene sulfides); phosphorus sulfided hydrocarbons (e.g., the reaction product of phosphorus sulfide with talpentine or methyl oleate); (For example, dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite,
Pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethylnaphthyl phosphite, oleyl-4-pentylphenyl phosphite, phenyl phosphite substituted with polypropylene (molecular weight 500) , Diisobutyl-substituted phenyl phosphite);
Exemplified by metal thiocarbamate (eg, zinc dioctyldithiocarbamate, barium heptylphenyldithiocarbamate).

Pour point depressants are a particularly useful type of additive often included in the lubricating oils described herein. The use of such pour point depressants in oil-based compositions to improve the low temperature properties of the oil-based compositions is known in the art. For example, CVSmalheer and
R. Kennedy Smith's "Lubricant Additives" (Lezius-Hiles Co.
See page 8 of the publisher, Cleveland, Ohio, 1967).

Examples of useful pour point depressants include polymethacrylates;
Polyacrylates; polyacrylamides; condensation products of haloparaffin waxes with aromatic compounds; vinyl carboxylate polymers; terpolymers of dialkyl fumarate, vinyl esters of fatty acids and alkyl vinyl ethers. Pour point depressants useful for the present invention, their method of preparation and their use are described in U.S. Pat.
No. 1; 2,015,748; 2,655,479; 1,815,022; 2,191,498
No. 2,666,746; 2,721,877; 2,721,878 and 3,250,
No. 715, the contents of which are hereby set forth in connection with their related disclosure.

Antifoams are used to reduce or prevent the formation of stable foam. Typical defoamers include silicone or organic polymers. Other antifoam compositions are "foam control agents" (Henry T. Kerner, Neusdata,
1976), pp. 125-162.

The lubricating oil composition of the present invention may also contain one or more commercially available viscosity improvers, especially when the lubricating oil composition is formulated into a multigrade oil. Viscosity modifiers are polymeric substances that are generally characterized as hydrocarbon-based polymers. The polymer is generally about 25,0
Number average molecular weight between 00 and 500,000, in most cases
It has a number average molecular weight between about 50,000 and 200,000.

Polyisobutylene is used as a viscosity improver in lubricating oils. Polymethacrylate (PMA) is prepared from a mixture of methacrylate monomers having different alkyl groups. Most PMAs are viscosity improvers as well as pour point depressants. The alkyl group can have from 1 to about 18
It can be either a straight chain or branched chain containing carbon atoms.

When small amounts of nitrogen-containing monomers are copolymerized with the alkyl methacrylate, the dispersing properties are also included in the product. Therefore, such products have multiple functions such as viscosity improving, pour point depressing and dispersing. Such products are indicated in the art as dispersion-type viscosity improvers or simply dispersion viscosity improvers.
Vinylpyridine, N-vinylpyrrolidone and N, N'-
Dimethylaminoethyl methacrylate is an example of a nitrogen-containing monomer. Polyacrylates obtained by the polymerization or copolymerization of one or more alkyl acrylates are also useful as viscosity improvers.

Ethylene-propylene copolymer (this is generally
) Can be prepared by copolymerizing ethylene and propylene using a known catalyst such as a Ziegler-Natta catalyst, generally in a solvent. The ratio of ethylene to propylene in the polymer affects the oil solubility, oil concentrating properties, low temperature viscosity, pour point depressing properties, and engine performance of the product. The usual range for the ethylene content is 45-60% by weight, typically 50% to about 55% by weight. Certain commercially available OCPs include ethylene, propylene and small amounts of non-conjugated dienes (eg, 1,
4-hexadiene). In the rubber industry, such terpolymers are designated as EPDM (ethylene-propylene-diene monomer). The use of OPC as a viscosity improver in lubricating oils has increased rapidly since almost 1970. OPC is currently one of the most widely used viscosity improvers in automotive oils.

Styrene and maleic anhydride are copolymerized in the presence of a free radical initiator, after which the copolymer is
Esters obtained by esterification with a mixture of _4-18 alcohols are also useful in automotive oils as viscosity improving additives. This styrene ester is considered to be a multifunctional added viscosity improver. The styrene ester, in addition to these viscosity modifying properties, is a pour point depressant, and when esterification is stopped before its completion, leaving unreacted anhydride or carboxylic acid groups,
Shows dispersion characteristics. These acid groups can then be converted to imides by reaction with primary amines.

Hydrogenated styrene-conjugated diene copolymers are another class of commercially available viscosity improvers for automotive oils. Examples of styrenes include styrene, α-methylstyrene, o
-Methylstyrene, m-methylstyrene, p-methylstyrene, n-tertiary butylstyrene and the like.
Preferably, the conjugated diene contains 4 to 6 carbon atoms. Examples of conjugated dienes include piperylene, 2,3-
Dimethyl-1,3-butadiene, chloroprene, isoprene and 1,3-butadiene are included, with isoprene and butadiene being particularly preferred. Mixtures of such conjugated dienes are useful.

The styrene content of such copolymers is from about 20% by weight to
It is in the range of about 70%, preferably about 40% to about 60% by weight. The aliphatic conjugated diene content of these copolymers is about
It ranges from 30% to about 80% by weight, preferably from about 40% to about 60% by weight.

These co-weights typically range from about 30,000 to about 500,00
It has a number average molecular weight in the range of 0, preferably about 50,000 to about 200,000. The weight average molecular weight of these copolymers is generally from about 50,000 to about 500,000, preferably from about 50,000 to about 30.
It is in the range of 0,000.

The hydrogenated copolymers described above are known from the prior art (e.g., U.S. Patent Nos. 3,551,336; 3,598,738; 3,554,911; 3,607,749).
Nos. 3,687,849 and 4,181,618), the contents of which are set forth herein with respect to the disclosure of polymers and copolymers useful as viscosity improvers in the oil compositions of the present invention. For example, U.S. Pat.
It describes a hydrogenated random butadiene-styrene copolymer, its preparation and hydrogenation. The disclosure of this patent is set forth herein. Hydrogenated styrene-butadiene copolymers useful as viscosity improvers in the lubricating oil compositions of the present invention are commercially available, for example, from BASF under the generic trademark "Glissoviscal". A particular example is a hydrogenated styrene-butadiene copolymer available under the name Glissoviscla 5260. This material has a molecular weight of about 120,000, as determined by gel permeation chromatography.
Hydrogenated styrene-isoprene copolymers useful as viscosity improvers are described, for example, under the general trademark "Shellvi
s "and commercially available from Shell Chemical Company. Shellivis 40, available from Shell Chemical Company, is a diblock copolymer of styrene and isoprene, which has a number average molecular weight of about 155,000, about 19 mole percent Having a styrene content and an isoprene content of about 81 mole percent.) Shellvis 50 from Shell Chemical Company
Has been identified as a diblock copolymer of styrene and isoprene, which has a number average molecular weight of about 100,000, a styrene content of about 28 mole percent and an isoprene content of about 72 mole percent.

The amount of polymer viscosity improver incorporated into the lubricating oil composition of the present invention can vary over a wide range. However, due to the performance of the carboxylic acid derivative component (B) (and certain carboxylic acid ester derivatives (E)) that, in addition to functioning as a dispersant, function as a viscosity improver, less than normal amounts Amount is used. Generally, the amount of polymer viscosity modifier included in the lubricating oil composition of the present invention can be on the order of 10% by weight, based on the weight of the final lubricating oil. In most cases,
The polymer viscosity modifier is present in a concentration of about 0.2% to about 8% by weight of the final lubricating oil, especially about 0.5% to about 6% by weight.
Used at a concentration of

The lubricating oils of the present invention can be prepared by dissolving or suspending the various components indicated in the base oil, along with certain other additives that may be employed. In most cases, the chemical components of the present invention will be diluted with a substantially inert, normally liquid, organic diluent (eg, mineral oil, naphtha, benzene, etc.) to form an additive concentrate. These concentrates usually comprise the additional components (A) to (C) described above.
Up to about 0.01% to about 80% by weight of one or more, and may further contain one or more of the other additives described above. For example, 15%, 20%, 30% or
50% or more concentrates may be used.

For example, on a chemical basis, from about 10% to about 50% by weight of the carboxylic acid derivative composition (B), and from about 0.01% to
It may contain about 15% by weight of the metal phosphorodithioate mixture (C). The concentrate also contains from about 1% to about 30% by weight of the carboxylic ester (E), and / or about 1% by weight.
From about 20% by weight of at least one neutral or basic alkaline earth metal salt (D).

Typical lubricating oil compositions of the present invention are illustrated in the following lubricating oil examples.

In the following lubricating oil examples I-XVIII, the percentages are by volume, and the percentages are the solutions of the indicated additives as used in forming the lubricating oil composition, diluted with ordinary oil. Indicates the amount of For example, lubricating oil I
Contains 6.5% by volume of the product of Example B-13, which is an oil solution of the indicated carboxylic acid derivative (B) containing 55% diluent oil.

According to the lubricating oil composition of the present invention, under the conditions of use, there is less tendency for degradation, thereby reducing abrasion and reducing the formation of undesirable precipitates such as: Such precipitates include, for example, burnish, sludge, carbon-containing materials, and resinous materials, which tend to adhere to various engine parts and reduce engine efficiency. Lubricating oils can also be formulated according to the present invention. This results in improved fuel consumption when used in passenger car crankcases. In certain embodiments, the lubricating oil may be formulated within the scope of the present invention and may pass all tests necessary for classification as an SG oil.

The lubricating oils of the present invention are also useful in diesel engines. Lubricating oil formulations meeting the requirements of the new diesel class CE can be prepared according to the present invention.

The performance characteristics of the lubricating oil composition of the present invention are evaluated by subjecting the lubricating oil composition to a number of engine oil tests. These tests are designed to evaluate various performance characteristics of engine oil. As noted above, in order for a lubricant to meet API Service Classification SG, it must pass certain engine oil tests. However, lubricating oil compositions that pass one or more individual tests are also useful in certain applications.

ASTM sequence, III E engine oil test, recently, SG engine oil high temperature wear, oil concentration,
And as a means of defining precipitate protection properties. The IIIE test, which is used in place of the Sequence IIID test, provides improved differences in hot camshaft and lifter wear protection and oil concentration control. The IIIE test utilizes a Buick 3.8LV-6 model engine. The engine operates on leaded fuel at 67.8 bhp and 3000 rpm for a maximum test time of 64 hours. A 230 lb valve spring load is used. Due to the high engine operating temperature, 100
% Glycol coolant is used. Coolant outlet temperature is maintained at 118 ° C and oil temperature is 30 psi oil pressure.
At 149 ° C. The air-fuel ratio is 16.5,
The gas leak rate is 1.6 cfm. Initial oil charge is 146 oz.

The test is performed at 8-hour check intervals with an oil level of 28
It ends when it reaches less than an ounce. Due to the low oil level, if the test ends 64 hours ago, this low oil level will generally leave the oil oxidized significantly throughout the engine, and at an oil check temperature of 49 ° C, it will Can not be discharged.
The viscosity is measured on an 8 hour oil sample. From this data, a curve of the rate of increase in viscosity over engine time is plotted. 40 ° C, 64 for API classification SG
Up to a 375% increase in viscosity, measured over time, is required. Engine sludge requirements are a minimum of 9.2, piston varnish is a minimum of 8.9, and minimum ringland deposit is 3.5 based on the CRC merit rate system. For a more detailed description of the recent Sequence III E test, see the “Sequence III D Surveillance Panel Report on Sequence III Tests for ASTM Oil Grade Panels”, dated November 30, 1987 and January 11, 1988. Has been revised).

Sequence III performed on lubricants XII and XIV
The results of the E test are summarized in Table V below.

The Ford Sequence VE test is described in the "ASTM Sludge and Wear Control Board Report and Sequence VD Surveillance Panel--Designated PV2 Test" dated October 13, 1987.

The test uses a 2.3 liter (140 CID) 4-cylinder overhead cam engine, which is equipped with a multipoint electric fuel injection system, and has a compression ratio of 9.5: 1. The test method uses the same format as a sequence VD test with a four hour cycle consisting of three different stages. Stage I,
The oil temperature (゜ F) at II and III is 155/210/115, and the water temperature (゜ F) at the three stages is 125/185/11
5 The oil filling capacity of the test is 106 oz. The rocker cover is coated for control of the upper engine temperature. The operating speed and load of the three stages are not different from the VD test. The gas leak rate in Stage I is from 1.8 CFM to 2.00
Increase to CFM. The test period is 12 days. PCV values are changed every 48 hours in this test.

At the final stage of the test, engine sludge, rocker cover sludge, piston burnish, average burnish and valve train wear are evaluated.

The results of Ford Sequence VE tests performed on the lubricating oils IV, XIV, XV and XVI of the present invention are summarized in Table VI below. The performance requirements of the SG classification are: engine sludge, 9.0 (minimum); rocker cover sludge,
7.0 (minimum); average varnish, 5.0 (minimum); piston varnish, 6.5 (minimum); VTW 15/5 (maximum).

This CRC L-38 test was developed by the Coordinating Research Council. This test method is used to determine the following properties of crankcase lubricants under high temperature operating conditions: oxidation resistance, tendency to corrosion, tendency to form sludge and varnish, and viscosity stability. this
The CLR engine is characterized by a certain design and is a single cylinder, liquid cooled, spark ignition engine. It operates at a constant speed and fuel flow. This engine has a one-quart crankcase capacity. This method requires a CLR single cylinder engine to operate at 3150 rpm, approximately 5 bhp, an oil gallery temperature of 290 ° F. and a coolant-out temperature of 200 ° F. for 40 hours. The test is stopped every 10 hours due to oil sampling and topping up (addition of oil). The viscosity of these oil samples was determined and the values are reported as part of the test results.

Certain copper-lead test bearings are weighed before and after testing to determine weight loss due to corrosion. After the test,
The engine is also evaluated for sludge and varnish deposits. The most important of these is the piston skirt varnish. The first performance criterion for the API service class SG is a bearing weight loss of up to 40 mg and a percentage of piston skirt varnish of at least 9.0.

Table VII below shows L-3 using three lubricants of this invention.
The results of the eight trials are summarized.

The Oldsmobile Sequence II D test is used to evaluate the corrosion properties of the rust properties of automotive oils.
This test and test conditions are described in ASTM Special Technical Publication 31.
5H (Part 1). This test relates to short-term travel services under winter driving conditions as encountered in the United States. Sequence II D is slow (1500
5.7 liter (350 CID) Vs from Oldsmobile with an engine coolant inlet temperature of 41 ° C and an engine coolant outlet temperature of 43 ° C under low load (25 bhp) conditions.
Use -8 engine operation. Subsequently, the test is operated at 1500 rpm for 2 hours using an engine coolant inlet temperature of 47 ° C and an engine coolant outlet temperature of 49 ° C. After changing the vaporizer and spark plug,
00 rpm) and medium load (100 bhp).
A final operation of 2 hours is performed using an engine coolant inlet temperature of 8 ° C. and an engine coolant outlet temperature of 93 ° C. As soon as the test is completed (32 hours), the engine is evaluated for rust using a CRC evaluation method. Many stuck valve lifters are also recorded. This gives an indication of the size of the rust. The minimum average rust percentage to pass the IID test is 8.5. When the lubricating oil compositions identified above as Lubricants VIII and XIV are used in the Sequence IID test, the average CRC rust percentages are 8.5 and 8.7, respectively.

The Caterpillar 1H2 test described in Part 2 of ASTM Special Technical Publication 509A is used to determine the effect of lubricating oil on caterpillar engines in terms of ring sticking, ring and cylinder wear, and piston deposit buildup. Can be This test involves running a single cylinder diesel engine test at a particularly high pressure for 480 hours at a constant speed of 1800 rpm and a constant heat input. A heat valve with a high heat input is 4950 btu / min and a heat valve with a low heat input is 4647 btu / min. The test oil is used as a lubricant. This diesel fuel is typically a refined diesel fuel containing 0.37 to 0.43% by weight of natural sulfur.

Upon completion of this test, the diesel engine was tested to determine which stack rings were present, the degree of wear on the cylinders and linear and piston rings, and the amount and nature of piston deposits present. To be tested. In particular, the top groove filling (TGF) and the weighed total defect (WTD), based on the coverage and location of the precipitate, were tested in this test as the first performance criteria for diesel lubricants. Be recorded. The target value for the 1H2 test is a maximum of 45 (vol%) TG after 480 hours.
F, and a WTD rate of up to 140.

The results of the Caterpillar 1H2 test performed on some lubricating oil compositions of the present invention are summarized in Table VII below.

Although the Caterpillar 1H2 test is considered as a suitable test for low-level diesel applications (API service classification CC), the Caterpillar 1G2 test described in Part 1 of ASTM Special Technical Publication 509A is more severe. It is related to the level of use (API service classification CD).
This IG2 test is similar to the Caterpillar 1H2 test except that the test conditions are more demanding. Heat input-
The high heat valve is 5850 btu / min and the heat input-low heat valve is 5490 but / min. This engine runs at 42bhp. The operating temperature is also higher: water from the cylinder head is about 88 ° C and oil to the bearing is about 96 ° C. The air inserted into the engine is maintained at about 124 ° C,
The temperature of the exhaust gas is 594 ° C. Due to the rigor of this diesel test, the target value is higher than 1H2. The maximum allowable top groove filling is 80 and the maximum WTD is 300.

The results of the Caterpillar 1G2 test performed with the lubricants IX and XIV of the present invention are summarized in Table IX below.

The Sequence VI test is used to match passenger car and low level truck oils to the API / -SAE / ASTM energy conservation category. In this test, General Motors 3.8LV under tightly controlled conditions
Operating the -6 engine, which allows an accurate measurement of the brake special fuel consumption (BSFC) to indicate the friction associated with the lubricant present in the engine. For the highest accuracy, modern microprocessor control and data acquisition / processing systems are used.

Each test proceeds with an engine / system assay using the following specific ASTM oils: SAE 20W-30 moly-amine friction modifier (FM), SAE 50
(LR), and SAE 20W-30 high standard oil (HR). After confirming a certain level of accuracy and certification, the candidate oil is poured into the engine without stopping and subjected to aging for 40 hours under moderate temperature, low load and constant conditions. At the end of ripening, the folded BSFC measurement is performed at a temperature range of low (150 ° F) to high (275 ° F), 1500 rpm, 8 bhp at each of the two test stages. These BSFC data are compared to the same measurements obtained with a new (unaged) control oil HR. This control oil is poured directly into the engine after the measurements of the aged candidate oil have been recorded.

Extremely high performance flushing oil (FO) to minimize the effects of additives left over by the candidate oil
Before this HR, quickly pour into the engine. Flash oil is also used during pretest engine qualification. The duration of the test is about 3.5 days, with an operating time of 65 hours.

The reduction in fuel consumption provided by this candidate oil is the percent change in individual stages (delta) (150 ° F and 275 ° F).
に お け る F)). In the five car test results, a transformation equation is used to represent the equivalent fuel economy improvement (EFEI) results, based on an overall test of the weighed test results.

The transformation used is as follows: For example, if a 3% improvement is observed at 150 ° F and a 6% improvement at 275 ° F, then the EFEI using the above conversion formula is 2.49%.

Sequence VI fuel efficiency engine oil dynamometer test (this is based on the lubricating oil composition of the invention
And XI)) are summarized in Table X below. The 1.5% target is the minimum percentage established to demonstrate fuel economy. The 2.7% target is the minimum improvement in fuel economy required for the API / SAE / ASTM energy conservation category.

The advantage of the lubricating oil composition of the present invention as a diesel lubricant is that the lubricant in Lubricating Examples XVI-XVIII is
Truck Technical Service Standard Test Method No.5GT 57 (This is
"Mack T-7: referred to as Diesel Engine Oil Viscosity Evaluation, August 31, 1984). This test, coupled with hands-on experience,
Designed. In this test, the Mack EM6-285 engine is operated at low speed, high torque, and constant conditions.
The engine is a direct injection, in-line, 6 cylinder, 4 stroke, turbocharged series, air-cooled, compression ignited engine (including a keystone ring). This evaluated output is 2300rpm
At a speed adjusted to 283bhp.

The test procedure consists of a test oil burst during the first commissioning period (after only a major replacement) and 1200 rpm
At 1080 ft / ib. Torque and 150 hours of constant operation. Do not replace or add oil. However, during the test, eight 4 ounce oil samples are periodically taken from the drain valve of the oil pan for analysis. Sixteen ounces of oil are removed at the oil drain valve before each four ounce sample is removed to clean the drain system. The sample of this wash is then returned to the engine after sampling. No replacement oil is added to the engine to replace the 4 ounce sample.

The kinematic viscosity is measured at 210 ° F at 100 and 150 hours of the test. Then, the “viscosity increase rate” is calculated. The viscosity increase rate is a value obtained by dividing the difference between the viscosity at 100 hours and the viscosity at 150 hours by 50. This value should preferably be less than 0.04. This can be seen as the study progresses
Reflects an increase in minimum viscosity.

Kinematic viscosity at 210 ° F. can be measured by two methods. In both methods, the sample is passed through a # 200 sieve before being subjected to a Canon Reverse Flow Viscometer. In the method of ASTM D-445, the viscometer is selected to obtain a flow time equal to or greater than 200 seconds. In the method described in the Mack T-7 specification, a Canon 300 viscometer is used for all viscosity measurements. The flow time of the latter method is typically less than 15%
50-100 seconds for W-40 diesel lubricant.

The results of the Mack T-7 test using three of the lubricants of the present invention are summarized in Table XI below: Although the invention has been described in terms of its more preferred embodiments, it should be understood that various modifications thereof will become apparent to those skilled in the art upon reading this specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10M 137: 10 129: 68 129: 74 129: 10 129: 72) C10N 10:02 10:04 10:06 10:08 10: 12 10:14 10:16 20:04 30:04 40:25 (56) References Table of International Publication No. 63-501018 (JP, A) US Patent 4577037 (US, A) US Patent 4495075 (US, A) US Patent 3691220 (US, A) U.S. Pat. No. 3,290,246 (US, A) British publication 1102032 (GB, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C10M 141/10 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (13)

(57) [Claims] A lubricating oil composition for an internal combustion engine, comprising:
The composition contains the following major amounts of (A), at least 2.0% by weight of (B), and from about 0.05% to about 5% by weight of (C): (A) an oil of lubricating viscosity; (B) at least one carboxyl produced by reacting (B-1) at least one substituted succinic acylating agent with at least one amine compound characterized by (B-2) An acid derivative composition; wherein the amine compound is characterized by the presence of at least one HN <group in its structure; wherein the substituted succinic acylating agent comprises a substituent and a succinic group. Wherein the substituent is derived from a polyalkene, wherein the polyalkene has an n value of 1300 to about 5000 and about 1.5 to about 4.5.
The acylating agent is characterized by a w / n value of
The structure is characterized by an average of at least 1.3 succinic groups present for each equivalent of substituent. (C) a mixture of metal salts of dihydrocarbyl phosphorodithioic acid; wherein at least one dihydrocarbyl phosphorodithioic acid has one of the hydrocarbyl groups (C-1)
Is an isopropyl group or a secondary butyl group, the other hydrocarbyl group (C-2) contains at least 5 carbon atoms; and all of the hydrocarbyl groups present in (C) At least about 20 mole percent is isopropyl groups, secondary butyl groups or mixtures thereof; provided that the lubricating oil composition contains no more than about 2.5% by weight of (B), At least about 25 mole percent of the hydrocarbyl groups of are isopropyl groups, secondary butyl groups, or mixtures thereof. 2. The method according to claim 1, further comprising the following (D):
(D) at least one of the at least one acidic organic compound
Species neutral or basic alkaline earth metal salts. 3. The lubricating oil composition according to claim 2, wherein said acidic organic compound (D) is a sulfur-containing acid, carboxylic acid, phosphorus-containing acid, phenol or a mixture thereof. 4. The method according to claim 1, further comprising the following (E):
And (2) at least one carboxylic ester derivative composition produced by the following reaction between (E-1) and (E-2): (E-1) At least one substituted succinic acylating agent containing a substituent and a succinic acid group, wherein the substituent has at least about 700 n; (E-2) at least one alcohol of the following general formula: R ³ (OH) _m where R ³ is a monovalent or polyvalent organic group attached to the —OH group via a carbon bond, and m is an integer from 1 to about 10. 5. The carboxylic ester derivative composition (E) prepared by reacting the acylating agent (E-1) with the alcohol (E-2), further comprising the following (E)
The lubricating oil composition according to claim 4, which is subjected to a reaction with (E-3): (E-3) at least one amine containing at least one HN <group. 6. A lubricating oil composition according to claim 1, comprising (A), (B) and (C): (A) a major amount of oil having lubricating viscosity; (B) (B) -1) at least one carboxylic acid derivative composition produced by reacting at least one substituted succinic acylating agent with at least one amine compound characterized by (B-2) At least 2.
0% by weight; the amine compound is characterized by the presence of at least one HN <group in its structure; wherein the substituted succinic acylating agent comprises a substituent and a succinic group. Wherein the substituent is derived from a polyalkene, wherein the polyalkene is characterized by an n value of 1300 to about 5000 and a w / n value of about 1.5 to about 4.5; Wherein at least 1.3 succinic groups are present on average for each equivalent of substituent; (C) a mixture of metal salts of dihydrocarbyl phosphorodithioic acid; In one of the dihydrocarbyl phosphorodithioic acids, one of the hydrocarbyl groups (C-1) is an isopropyl group or a secondary butyl group, and the other hydrocarbyl group (C-2) has at least
And the lubricating oil composition comprises:
It contains at least about 0.05% by weight of isopropyl groups, secondary butyl groups or mixtures thereof derived from (C); provided that the lubricating oil composition contains no more than about 2.5% by weight of (B) When present, the lubricating oil composition contains at least about 0.06% by weight of the isopropyl groups, secondary butyl, or mixtures thereof. 7. The method according to claim 6, further comprising the following (D):
(D) at least one of the at least one acidic organic compound
Species neutral or basic alkaline earth metal salts. 8. The lubricating oil composition according to claim 1, comprising at least about 2.5% by weight of the carboxylic acid derivative composition (B). 9. The lubricating oil composition according to claim 1, wherein said n value in (B) is at least about 1500. 10. The w / n value of (B) is from about 1.5 to about 4.0.
The lubricating oil composition according to claim 1, wherein 11. The other hydrocarbyl group (C-2)
Is a primary aliphatic group containing from about 6 to about 13 carbon atoms. 12. The method according to claim 1, which comprises at least about 0.08% by weight of the isopropyl groups derived from (C).
The lubricating oil composition according to the above. 13. The method of claim 1, wherein said hydrocarbyl group (C-1) is an isopropyl group, and wherein at least about 25 mole percent of all of said hydrocarbyl groups present in (C) are isopropyl groups. The lubricating oil composition according to the above.